US20180044609A1 - Lubricating oil composition for internal-combustion engine, and method for reducing friction in gasoline engine - Google Patents
Lubricating oil composition for internal-combustion engine, and method for reducing friction in gasoline engine Download PDFInfo
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- US20180044609A1 US20180044609A1 US15/559,579 US201615559579A US2018044609A1 US 20180044609 A1 US20180044609 A1 US 20180044609A1 US 201615559579 A US201615559579 A US 201615559579A US 2018044609 A1 US2018044609 A1 US 2018044609A1
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- lubricating oil
- oil composition
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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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
- 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
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
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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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/54—Amines
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- 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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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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
- 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
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- 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
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/38—Polyoxyalkylenes esterified
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- 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
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- 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
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- 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
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- 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
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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- 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
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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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
- 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
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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
- C10N2010/04—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
- 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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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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
- 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
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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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
- 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
- C10N2030/45—Ash-less or low ash content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- 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
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- C10N2230/02—
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Definitions
- the present invention relates to a lubricating oil composition for an internal combustion engine.
- PTL 1 proposes use of a molybdenum compound such as MoDTC that is a typical one as a method for friction reduction, as a friction reducer.
- PTLs 2 and 3 propose use of a boron-containing compound prepared by heating and stirring an organic compound having a hydroxyl group and an amino group, and a boric acid or a boric acid derivative in a high-temperature environment, as a friction reducer.
- PTL 4 proposes a lubricating oil composition prepared by blending a nonionic surfactant having an HLB value of 15 or more, into a lubricant base oil.
- PTL 5 proposes a lubricating oil composition for use in a friction-type driving force transmitting device, containing a specific amine compound.
- the friction reducer and the lubricating oil composition proposed in PTLs 2 to 5 are silent in friction reduction in a low-temperature range.
- an ash-free friction reducer such as a glycerin monooleate or the like has been used.
- an ash-free friction reducer could not exhibit a friction-reducing effect in a practical temperature range of 80° C. or higher.
- a lubricating oil composition for internal combustion engines is required to have a high friction-reducing effect from a low-temperature range at engine starting to a practical temperature range of 80° C. or higher, and to have a low-ash content.
- a molybdenum-based friction reducer and an ash-free friction reducer could hardly satisfy the requirements.
- a lubricating oil composition using an ash-free friction reducer that can realize a sufficient friction-reducing effect from a low-temperature range at engine starting to even a practical temperature range of 80° C. or higher is desired.
- An object of the present invention is to provide a lubricating oil composition for internal combustion engines that can realize a sufficient friction-reducing effect not only in a low-temperature range assuming engine starting but also in a practical temperature range of 80° C. or higher.
- an aspect of the present invention provides a lubricating oil composition for internal combustion engines, which contains a surfactant having an alkylene oxide as the constituent unit and having an HLB value of 7 or more and less than 15, and a lubricant base oil.
- the lubricating oil composition for internal combustion engines of the present invention can better a friction-reducing effect from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher, and eventually can better fuel-saving performance.
- the lubricating oil composition for internal combustion engines of this embodiment contains a surfactant having an alkylene oxide as the constituent unit and having an HLB value of 7 or more and less than 15, and a lubricant base oil.
- the lubricating oil composition for internal combustion engines of this embodiment contains a surfactant having an alkylene oxide as the constituent unit and having an HLB value of 7 or more and less than 15.
- a surfactant having an HLB value falling within the above range but not having an alkylene oxide as the constituent unit tends to result in insufficient friction reduction.
- a surfactant having an alkylene oxide as the constituent unit but having an HLB value of less than 7 poorly adsorbs to a metal surface and is therefore poor in friction reduction.
- a surfactant having an alkylene oxide as the constituent unit but having an HLB value or more than 15 poorly dissolves in a lubricant base oil and is therefore extremely difficult to use.
- an amine compound As the above surfactant, various kinds of surfactants can be used, but from the viewpoint of friction reduction owing to adsorption to metal surfaces, an amine compound, an amide compound and the like in which an alkylene oxide bonds to the nitrogen atom are preferred. Among these, an amine compound is preferred, and among amine compounds, a tertiary amine is preferred.
- the surfactant of a tertiary amine compound includes compounds represented by the following general formula (I).
- the compounds represented by the general formula (I) are favorable in the point that the compounds have the above-mentioned effect and the ash content therein is 0% by mass:
- the alkyl group and the alkenyl group for R 1 and R 2 may be linear, branched or cyclic, but is preferably linear.
- R 1 and R 2 each are preferably an alkenyl group.
- the alkyl group and the alkenyl group for R 1 each preferably have 12 to 18 carbon atoms.
- the oxyalkylene group for A 1 O and A 2 O preferably has 2 to 3 carbon atoms, more preferably 2 carbon atoms.
- n 1 and n 2 each are independently an integer of 2 to 10, more preferably 3 to 7.
- n 1 +n 2 is preferably 8 to 12, more preferably 9 to 11.
- oxyalkylene groups having a different number of carbon atoms may bond to each other randomly or in blocks.
- (A 1 O) n1 and (A 2 O) n2 may be those of ethylene oxide (EO) groups and propylene oxide (PO) groups bonding to each other randomly or in blocks.
- a tertiary amine of the general formula (I) is used as the surfactant, those of the same kind or those of different kinds as combined may be used.
- the same kind means that R 1 , R 2 and others in the above general formula (I) are all the same. Different kinds mean that one or more of R 1 , R 2 and others in the above general formula (I) differs from each other.
- the proportion of the mass of the tertiary amine of the general formula (I) where R 1 and R 2 each an alkenyl group to the total mass of the tertiary amine is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more.
- tertiary amines of the general formula (I) where R 1 all has the same number of carbon atoms are preferably used.
- the tertiary amine of the general formula (I) contains R 2 those where additionally R 2 all has the same number of carbon atoms are preferably used.
- a polyoxyalkylene fatty acid ester is also preferred.
- the number of carbon atoms constituting the oxyalkylene group of the polyoxyalkylene fatty acid ester is preferably 2 to 4, more preferably 2 to 3, even more preferably 2.
- oxyalkylene groups differ in point of the number of constituent carbon atoms may bond to each other randomly or in blocks.
- the average addition molar number of the oxyalkylene groups is an integer of 2 to 10, more preferably 3 to 7.
- the number of carbon atoms of constituting the constituent unit derived from the fatty acid of the polyoxyalkylene fatty acid ester is preferably 8 to 28, more preferably 14 to 22, even more preferably 16 to 20.
- the polyoxyalkylene fatty acid ester of the type includes a polyoxyethylene oleate, a polyoxyethylene stearate, etc.
- the molecular weight of the above-mentioned surfactant is, from the viewpoint of reducing friction and making friction reduction consistent with detergency, preferably in a range of 350 to 950 g/mol, more preferably in a range of 440 to 940 g/mol.
- the molecular weight of the surfactant is one measured on a mass spectrum according to liquid chromatography mass spectrometry (LC/MS). Specifically, a range in which a peak of mass/charge ratio (m/z) of the surfactant appears is considered as a range of the molecular weight (g/mol) of the surfactant.
- LC/MS liquid chromatography mass spectrometry
- the surfactant contains 0% by mass of ash.
- the surfactant is contained in the lubricating oil composition for internal combustion engines preferably in an amount of 0.01 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, even more preferably 0.2 to 1.0% by mass.
- the content of the surfactant When the content of the surfactant is 0.01% by mass or more, friction can be reduced from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher. When the content of the surfactant is 2.0% by mass or less, reduction in detergency can be readily prevented from lowering while maintaining friction reduction.
- the lubricating oil composition for internal combustion engines of this embodiment further contains a boron-modified succinimide.
- the composition can reduce friction more efficiently from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher and can make a detergency of the composition good.
- the boron-modified succinimide includes those prepared by boronating an alkenyl or alkylsuccinic acid monoimide or an alkenyl or alkylsuccinic acid bisimide.
- the alkenyl or alkylsuccinic acid monoimide includes compounds represented by the following general formula (II).
- the alkenyl or alkylsuccinic acid bisimide includes compounds represented by the following general formula (III).
- R 3 , R 5 and R 6 each represent an alkenyl group or an alkyl group, and the weight-average molecular weight thereof is preferably 500 to 3,000, more preferably 1,000 to 3,000.
- R 3 , R 5 and R 6 When the weight-average molecular weight of R 3 , R 5 and R 6 is 500 or more, the solubility of the compound in a lubricant base oil is good. When 3,000 or less, the compound is expected to adequately exhibit the effect thereof. R 5 and R 6 may be the same or different.
- R 4 , R 7 and R 8 each represent an alkylene group having 2 to 5 carbon atoms, and R 7 and R 8 may be the same or different.
- n3 represents an integer of 1 to 10
- n4 represents 0 or an integer of 1 to 10.
- n3 is preferably 2 to 5, more preferably 2 to 4.
- n3 is 2 or more, the compound is expected to exhibit more easily the effect of the boron-modified succinimide.
- n3 is 5 or less, the solubility of the compound in a lubricant base oil is bettered more.
- n4 is preferably 1 to 6, more preferably 2 to 6.
- n4 is 1 or more, the compound is expected to adequately exhibit the effect of thereof.
- n4 is 6 or less, the solubility of the compound in a lubricant base oil is bettered more.
- the alkenyl group includes a polybutenyl group, a polyisobutenyl group, an ethylene-propylene copolymer.
- the alkyl group includes those prepared by hydrogenating these.
- a polybutenyl group or a polyisobutenyl group is a preferred alkenyl group.
- the polybutenyl group is preferably one prepared through polymerization of a mixture of 1-butene and isobutene, or polymerization of high-purity isobutene.
- Specific examples of a preferred alkyl group include those prepared by hydrogenating a polybutenyl group or a polyisobutenyl group.
- the boron-modified succinimide may be obtained, for example, by reacting a polyolefin and a maleic anhydride to give an alkenylsuccinic anhydride (A), separately reacting a polyamine and a boron compound to give an intermediate (B), and reacting the alkenylsuccinic anhydride (A) and the intermediate (B) for imidation.
- 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-modified succinimide may also be produced by treating an alkenyl or alkylsuccinic acid monoimide or an alkenyl or alkylsuccinic acid bisimide not containing boron, with a boron compound.
- olefin monomer to form the above-mentioned polyolefin one alone or two or more kinds of ⁇ -olefins having 2 to 8 carbon atoms may be used either singly or as combined.
- a mixture of isobutene and 1-butene is preferably used.
- the polyamine includes simple diamines such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, etc.; polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, pentapenthylenehexamine, etc.; piperazine derivatives such as aminoethylpiperazine, etc.
- the boron compound includes boric acid, boric acid salts, boric acid esters, etc.
- the boric acid includes orthoboric acid, metaboric acid, paraboric acid, etc.
- the boric acid salt includes ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, etc.
- the boric acid ester includes monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, tributyl borate, etc.
- the ratio of the boron atom amount to the nitrogen atom amount contained in the boron-modified succinimide is, from the viewpoint of friction reduction, preferably 0.6 or more on a mass standard, more preferably 0.7 or more, even more preferably 0.8 or more.
- the B/N ratio is, though not specifically limited thereto, preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.3 or less.
- the boron-modified succinimide contains a large amount of a 3-coordinated boron-modified succinimide, and specifically contains a 3-coordinated boron-modified succinimide in a ratio by mol of 0.50 or more relative to the total amount of the 3-coordinated and 4-coordinated boron-modified succinimides, more preferably in a ratio by mol of 0.60 or more, even more preferably 0.65 or more.
- the ratio of the 3-coordinated boron-modified succinimide and the 4-coordinated boron-modified succinimide may be measured, for example, through 11 B-NMR based on BF 3 .OEt 2 standard (0 ppm).
- 11 B-NMR a peak for the 3-coordinated boron-modified succinimide appears at 5 to 25 ppm, and a peak for the 4-coordinated boron-modified succinimide appears at ⁇ 10 to 5 ppm, and therefore, by calculating the integrated vale of each peak, the above-mentioned ratio can be calculated.
- the content of the boron-modified succinimide is preferably 0.1 to 15.0% by mass in the lubricating oil composition for internal combustion engines, more preferably 0.2 to 10.0% by mass, even more preferably 0.5 to 5.0% by mass, still more preferably 0.5 to 2.0% by mass.
- the lubricating oil composition can reduce friction more efficiently from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher and can better detergency.
- the boron atom-equivalent content of the boron-modified succinimide is preferably 0.2% by mass or less in the lubricating oil composition for internal combustion engines, more preferably 0.001 to 0.05% by mass, even more preferably 0.005 to 0.03% by mass.
- the lubricating oil composition can reduce friction more efficiently from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher and can better detergency.
- the ratio by mass of the content of the surfactant to the content of the boron-modified succinimide is preferably 100 or less, more preferably 20 or less, even more preferably 5 or less.
- the lubricating oil composition can reduce friction more efficiently from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher and can better detergency.
- the ratio by mass of the content of the surfactant to the content of the boron atom-equivalent content of the boron-modified succinimide is preferably 1 or less, more preferably 0.2 or less, even more preferably 0.05 or less.
- the ratio by mass falls within the above range, the lubricating oil composition can reduce friction more efficiently from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher and can satisfy more readily both friction reduction and detergency.
- the lubricating oil composition for internal combustion engines of this embodiment further contains a poly(meth)acrylate as a viscosity index improver.
- the lubricating oil composition can improve fuel-saving performance more efficiently in addition to the effect of improving fuel-saving performance owing to friction reduction by the surfactant and the boron-modified succinimide therein.
- the monomer to constitute the poly(meth)acrylate is an alkyl (meth)acrylate and is preferably an alkyl (meth)acrylate having a linear alkyl group with 1 to 18 carbon atoms or a branched alkyl group with 3 to 34 carbon atoms.
- Preferred examples of the monomer to constitute alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetra(meth)acrylate, hexa(meth)acrylate, octadecyl (meth)acrylate, etc. Two or more kinds of these monomers may be used to give a copolymer.
- the alkyl group of these monomers may be linear or branched.
- the alkyl (meth)acrylate having a branched alkyl group with 3 to 34 carbon atoms includes isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, 2-butyloctyl (meth)acrylate, 2-hexyldecyl (meth)acrylate, 2-octyldodecyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, 2-dodecylhexadecyl (meth)acrylate, 2-tetradecyloctadecyl (meth)acrylate.
- the poly(meth)acrylate is preferably one having a weight-average molecular weight of 100,000 to 600,000, more preferably 15,000 300,000.
- weight-average molecular weight is meant to indicate a polystyrene-equivalent molecular weight measured through gel permeation chromatography (GPC).
- SSI of the poly(meth)acrylate is preferably 30% or less, more preferably 1 to 28%.
- the poly(meth)acrylate may have SSI of 30% or less.
- SSI means a shear stability index, and indicates the decomposition resistance of the poly(meth)acrylate. Having a larger SSI value, the polymer is more unstable against shearing and is decomposed more readily.
- Kv 0 is a value of 100° C. kinematic viscosity of a mixture prepared by adding a poly(meth)acrylate to a base oil.
- Kv 1 is a value of 100° C. kinematic viscosity of a mixture prepared by adding a poly(meth)acrylate to a base oil after the mixture has made to pass through a high-shear Bosch diesel injector for 30 cycles according to a process of ASTM D6278.
- Kv oil is a value of 100° C. kinematic viscosity of a base oil.
- As the base oil Group-II base oil having a 100° C. kinematic viscosity of 5.35 mm 2 /s and a viscosity index of 105 is used.
- the content of the poly(meth)acrylate is, from the viewpoint of fuel-saving performance, preferably 1 to 15% by mass in the lubricating oil composition for internal combustion engines, more preferably 2 to 10% by mass, even more preferably 3 to 8% by mass.
- the lubricating oil composition for internal combustion engines of this embodiment further contains a molybdenum compound.
- the molybdenum compound includes MoDTC (molybdenum dialkyldithiocarbamate), MoDTP (molybdenum dialkyldithiophosphate), etc.
- the content of the molybdenum compound is preferably 2.0% or less by mass in the lubricating oil composition for internal combustion engines, more preferably 0.1 to 1.0% by mass.
- the lubricant base oil includes a mineral oil and/or a synthetic oil.
- the mineral oil includes a paraffin-base mineral oil, an intermediate-base mineral oil, a naphthene-base mineral oil and the like produced through ordinary purification such as solvent purification, hydrogenation purification, etc.; a wax-isomerized oil produced through isomerization of a wax such as a wax (gas-to-liquid gas) produced according to a Fischer Tropsch process or the like, a mineral oil wax, etc.
- the synthetic oil includes a hydrocarbon synthetic oil, an ether synthetic oil, etc.
- the hydrocarbon synthetic oil includes ⁇ -olefin oligomers or hydrides thereof such as a polybutene, a polyisobutylene, a 1-octene oligomer, a 1-decene oligomer, an ethylene-propylene copolymer, etc.; alkylbenzenes, alkylnaphthalenes, etc.
- the ether synthetic oil includes polyoxyalkylene glycols, poly phenyl ethers, etc.
- the lubricant base oil may be a single system using one kind of the above-mentioned mineral oils and synthetic oils, or may also be a mixed system, such as a mixture prepared by mixing two or more kinds of mineral oils, a mixture prepared by mixing two or more kinds of synthetic oils, or a mixture prepared by mixing one or more kinds of mineral oils and one or more kinds of synthetic oils.
- lubricant base oil use of one or more kinds selected from mineral oils and synthetic oils classified in Group 3 or Group 4 in base oil classification by American Petroleum Institute is preferred.
- the content of the lubricant base oil is preferably 70% by mass or more and less than 100% by mass in the lubricating oil composition for internal combustion engines, more preferably 75% by mass or more and 95% by mass or less, even more preferably 80% by mass or more and 90% by mass or less.
- the lubricating oil composition for internal combustion engines of this embodiment may contain additives such as a metallic detergent, an antioxidant, an anti-wear agent, etc.
- the content of these additives is each preferably 0.01 to 5% by mass relative to the total amount of the lubricating oil composition for internal combustion engines.
- the lubricating oil composition for internal combustion engines of this embodiment is, from the viewpoint of friction reduction from a low-temperature range assuming engine starting to a practical temperature range of 80° C. or higher, preferably such that the 40° C. kinematic viscosity, the 100° C. kinematic viscosity and the 150° C. HTHS viscosity thereof each fall within the following range.
- the 40° C. kinematic viscosity is preferably 20 to 40 mm 2 /s, more preferably 30 to 35 mm 2 /s.
- the 100° C. kinematic viscosity is preferably 3.0 to 12.5 mm 2 /s, more preferably 4.0 to 9.3 mm 2 /s.
- the 150° C. HTHS viscosity is preferably 1.4 to 2.9 mPa ⁇ s, more preferably 1.7 to 2.9 mPas.
- the kinematic viscosity is measured according to JIS K2283.
- the HTHS viscosity is measured according to ASTM D4683 using a TBS viscometer (tapered bearing simulator viscometer), at an oil temperature of 100° C., at a shear rate of 10 6 /s, at a rotation number (motor) of 3000 rpm, and with a distance (rotor-stator distance) of 3 ⁇ m.
- the lubricating oil composition for internal combustion engines of this embodiment can be favorably used for various internal combustion engines for four-wheel cars, two-wheel cars, etc.
- the composition is especially favorably used for gasoline engines.
- the friction reducing method for internal combustion engines of this embodiment includes adding the lubricating oil composition for internal combustion engines of this embodiment mentioned above, to an internal combustion engine.
- the friction-reducing effect can be bettered from a low-temperature range assuming engine staring to a practical temperature range of 80° C. or higher, and eventually fuel-saving performance can be thereby bettered.
- the above-mentioned effects can be especially favorably bettered.
- Lubricating oil compositions for internal combustion engines of Examples, Comparative Examples and Reference Example were prepared according to the compositional ratio shown in Table 1.
- the lubricating oil compositions for internal combustion engines of Examples, Comparative Examples and Reference Examples were all so controlled as to have an HTHS viscosity at 150° C. of 2.6 mPa ⁇ s.
- the 40° C. kinematic viscosity and 100° C. kinematic viscosity of each lubricating oil composition for internal combustion engines were measured.
- Tester MTM (Mini Traction Machine) tester, manufactured by PCS Instruments Corporation Test Piece: Standard test piece Rubbing Time: 2 hours
- Detector Photodiode array detector, evaporative light scattering detector
- Polyoxyalkylene fatty acid ester (HLB value: 11.1, number of carbon atoms of oxyalkylene group: 2, average addition molar number of oxyalkylene group: 5, number of carbon atoms of constituent unit derived from fatty acid: 18)
- Ethomeen O/12 manufactured by Lion Akzo Corporation
- MoDTC having an Mo content of 0.07% by mass
- Phenol-based antioxidant trade name: IRGANOX-L 135, manufactured by BASF Corporation
- the lubricating oil compositions for internal combustion engines of Examples 1 to 4 are excellent in the friction-reducing effect in a practical temperature range of 80° C. or higher though using an ash-free friction reducer.
- the lubricating oil composition for internal combustion engines of Example 3 using both a surfactant having an alkylene oxide as the constituent unit and having an HLB value of 7 or more and less than 15, and a boron-modified succinimide is extremely excellent in the above-mentioned effect.
- test temperature was set at 300° C., and the other conditions followed JPI-5S-55-99.
- JPI-5S-55-99 the glass tube after the test was scored from point 0 (black) to point 10 (colorless) at intervals of 0.5, and evaluated in 21 ranks. A larger number means better detergency
- the lubricating oil composition for internal combustion engines of this embodiment can be favorably used for various internal combustion engines for four-wheel cars, two-wheel cars, etc.
- the composition is especially favorably used for gasoline engines.
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- Lubricants (AREA)
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JP2015059666 | 2015-03-23 | ||
JP2015-059666 | 2015-03-23 | ||
PCT/JP2016/057465 WO2016152540A1 (ja) | 2015-03-23 | 2016-03-09 | 内燃機関用潤滑油組成物及びガソリンエンジンの摩擦低減方法 |
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US15/559,579 Abandoned US20180044609A1 (en) | 2015-03-23 | 2016-03-09 | Lubricating oil composition for internal-combustion engine, and method for reducing friction in gasoline engine |
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US (1) | US20180044609A1 (de) |
EP (1) | EP3275979A4 (de) |
JP (1) | JPWO2016152540A1 (de) |
CN (1) | CN107406794A (de) |
WO (1) | WO2016152540A1 (de) |
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US4704217A (en) * | 1986-08-20 | 1987-11-03 | Texaco Inc. | Gasoline crankcase lubricant |
AU8273887A (en) * | 1986-11-07 | 1988-06-01 | Lubrizol Corporation, The | Sulfur-containing compositions, lubricant, fuel and functional fluid compositions |
CA2030481C (en) * | 1990-06-20 | 1998-08-11 | William B. Chamberlin, Iii | Lubricating oil compositions for meoh-fueled diesel engines |
CA2243113A1 (en) * | 1997-09-23 | 1999-03-23 | Garry George Moore | Grease containing alkoxylated amine corrosion inhibitors |
JP4095750B2 (ja) * | 1999-08-30 | 2008-06-04 | 東燃ゼネラル石油株式会社 | 内燃機関用潤滑油組成物 |
JP4822473B2 (ja) * | 2001-04-02 | 2011-11-24 | 東燃ゼネラル石油株式会社 | 内燃機関用潤滑油組成物 |
JP4931299B2 (ja) * | 2001-07-31 | 2012-05-16 | Jx日鉱日石エネルギー株式会社 | 潤滑油組成物 |
US20070184991A1 (en) * | 2002-01-31 | 2007-08-09 | Winemiller Mark D | Lubricating oil compositions with improved friction properties |
JP3965694B2 (ja) * | 2003-05-27 | 2007-08-29 | 日産自動車株式会社 | 低摩擦摺動カム・フォロワの組合せ及びこれに用いる潤滑油組成物 |
EP1482190B1 (de) * | 2003-05-27 | 2012-12-05 | Nissan Motor Company Limited | Wälzkörper |
JP4511154B2 (ja) * | 2003-11-11 | 2010-07-28 | 新日本石油株式会社 | エンジン油用潤滑油組成物 |
JP5175462B2 (ja) * | 2006-09-04 | 2013-04-03 | 出光興産株式会社 | 内燃機関用潤滑油組成物 |
JP5349088B2 (ja) * | 2009-03-09 | 2013-11-20 | コスモ石油ルブリカンツ株式会社 | ガスエンジン用エンジン油組成物 |
JP5990749B2 (ja) * | 2012-03-16 | 2016-09-14 | 出光興産株式会社 | 潤滑油組成物、該潤滑油組成物を用いた摺動機構 |
US9499763B2 (en) * | 2012-12-21 | 2016-11-22 | Afton Chemical Corporation | Additive compositions with plural friction modifiers |
JP6072605B2 (ja) * | 2013-05-17 | 2017-02-01 | 昭和シェル石油株式会社 | 内燃機関用潤滑油組成物 |
JP5807833B1 (ja) * | 2015-05-16 | 2015-11-10 | 有限会社タービュランス・リミテッド | 潤滑油剤用の添加剤、及び潤滑油剤組成物 |
-
2016
- 2016-03-09 EP EP16768443.0A patent/EP3275979A4/de not_active Withdrawn
- 2016-03-09 JP JP2017508200A patent/JPWO2016152540A1/ja active Pending
- 2016-03-09 US US15/559,579 patent/US20180044609A1/en not_active Abandoned
- 2016-03-09 WO PCT/JP2016/057465 patent/WO2016152540A1/ja active Application Filing
- 2016-03-09 CN CN201680017222.1A patent/CN107406794A/zh active Pending
Non-Patent Citations (2)
Title |
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Chamberlin III US Patent no 5,422,022 * |
DiBiase US Patent no 5,141,658 * |
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WO2016152540A1 (ja) | 2016-09-29 |
EP3275979A1 (de) | 2018-01-31 |
EP3275979A4 (de) | 2018-08-08 |
CN107406794A (zh) | 2017-11-28 |
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