Classifications

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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
  • 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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  • 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
  • C10M133/56—Amides; Imides
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  • 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
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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
  • 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
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  • 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
  • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/02—Unspecified siloxanes; Silicones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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
  • C10N2030/44—Boron free or low content boron compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/45—Ash-less or low ash content
• • 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 internal combustion engines which can exhibit a good wear resistance for aluminum materials even when reducing a phosphorus content and a content of a metal component derived from a metal-based detergent in the composition.
• parts of an engine or a transmission are formed of a nonferrous metal material for reducing a weight thereof.
• a nonferrous metal material for reducing a weight thereof.
• an aluminum alloy in particular, an Al—Si alloy
• the conventional engine oils contain anti-wear agents such as zinc dithiophosphate (ZnDTP) which are intended to mainly cause a reaction for forming a coating film on Fe. Therefore, there is such a fear that the oils are deteriorated in wear resistance for aluminum materials such as Al—Si alloy.
• Patent Document 1 JP 2010-528155A
• an object of the present invention is to provide a lubricating oil composition for internal combustion engines which is excellent in wear resistance for aluminum materials and can be considerably reduced in content of ZnDTP having a large phosphorus content or a metallic detergent while maintaining a good wear resistance for aluminum materials.
• the present inventors have found that when controlling a nitrogen content and a boron content derived from an imide-based dispersant and a boronated imide-based dispersant in the composition, the above object can be achieved.
• the present invention has been accomplished on the basis of the above finding.
• the present invention relates to the following aspects.
• R 1 and R 2 are each independently a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom; and A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 12 carbon atoms.
• a lubricating oil composition for internal combustion engines which is excellent in wear resistance for aluminum materials and can be considerably reduced in content of ZnDTP having a large phosphorus content or a metallic detergent while maintaining a good wear resistance for aluminum materials.
• a lubricating oil composition for internal combustion engines which is capable of reducing an adverse influence on an exhaust gas post-treatment device while maintaining a good wear resistance for aluminum materials.
• the present invention relates to a lubricating oil composition for internal combustion engines, including a boronated imide-based dispersant, or the boronated imide-based dispersant and a non-boronated imide-based dispersant, in which a boron content (B % by mass) derived from the boronated imide-based dispersant, and a nitrogen content (N % by mass) derived from the boronated imide-based dispersant or derived from the boronated imide-based dispersant and the non-boronated imide-based dispersant satisfy the following formula (I):
• composition capable of satisfying the above formula (I) can be enhanced in wear resistance.
• the boronated imide-based dispersant is used, if required, in combination with the non-boronated imide-based dispersant.
• the non-boronated imide-based dispersant is usually referred to merely as an imide-based dispersant.
• an imide-based dispersant there may be suitably used polybutenyl succinic acid imides.
• the polybutenyl succinic acid imides include compounds represented by the following general formulae (1) and (2).
• PIB represents a polybutenyl group.
• the number-average molecular weight of PIB is usually from 800 to 3500 and preferably from 900 to 2000. When the number-average molecular weight of PIB is 800 or more, there is no fear that the resulting composition is deteriorated in dispersibility. When the number-average molecular weight of PIB is 3500 or less, there is no fear that the resulting composition is deteriorated in storage stability.
• n is usually an integer of from 1 to 5 and preferably from 2 to 4.
• n lies within the above-specified range, there is no fear that the resulting composition is deteriorated in dispersibility.
• the method for producing the above polybutenyl succinic acid imides is not particularly limited, and the polybutenyl succinic acid imides may be produced by any known methods. For example, polybutene and maleic anhydride are reacted with each other at a temperature of from 100 to 200° C. to obtain polybutenyl succinic acid, and then the thus obtained polybutenyl succinic acid is reacted with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine to obtain the polybutenyl succinic acid imides.
• a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine
• boronated imide-based dispersant used in the present invention there may be mentioned those boronated polybutenyl succinic acid imides obtained by reacting the above non-boronated imide-based dispersant represented by the above general formula (1) or (2) with a boron compound.
• Examples of the boron compound include boric acid, a boric acid salt and a boric acid ester.
• Specific examples of the boric acid include orthoboric acid, metaboric acid and paraboric acid.
• Suitable examples of the boric acid salt include ammonium salts, e.g., ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate.
• Suitable examples of the boric acid ester include esters of boric acid and an alkyl alcohol (preferably having 1 to 6 carbon atoms), for example, monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate and tributyl borate.
• the mass ratio of the boron content B to the nitrogen content N(B/N) in the boronated polybutenyl succinic acid imides is preferably from 0.1 to 3 and more preferably from 0.2 to 2.
• the contents of the above boronated succinic acid imide-based dispersant and non-boronated succinic acid imide-based dispersant are not particularly limited as long as they can satisfy the above formula (I), and are each preferably from 0.1 to 15% by mass and more preferably from 0.5 to 10% by mass.
• the resulting composition can exhibit a good detergency and a good dispersibility.
• the resulting composition can exhibit an effect of enhancing a detergency and a dispersibility thereof corresponding to the increased content.
• a phosphorus content (P % by mass) and a content of a metal component (M % by mass) derived from a metallic detergent satisfy any of the following requirements A to C.
• P % by mass a phosphorus content
• M % by mass a content of a metal component derived from a metallic detergent
• the phosphorus content in the lubricating oil composition is less than 0.03% by mass on the basis of a total amount of the composition, whereas the content of the metal component derived from the metallic detergent in the lubricating oil composition is less than 0.05% by mass on the basis of a total amount of the composition.
• the phosphorus content in the composition is less than 0.03% by mass, poisoning of active sites of a three-way catalyst can be suppressed, so that a service life of the catalyst can be extended. Therefore, the phosphorus content in the composition is preferably 0.01% by mass or less, more preferably 0.005% by mass or less and still more preferably 0.001% by mass or less.
• the content of the metal component derived from the metal-based detergent in the composition is less than 0.05% by mass, deposition of ashes derived from the metal component on DPF can be suppressed, so that a service life of DPF can be extended. Therefore, the content of the metal component in the composition is preferably 0.01% by mass or less, more preferably 0.005% by mass or less and still more preferably 0.001% by mass or less.
• zinc dithiophosphate (ZnDTP) extensively used as an extremely excellent anti-wear agent in conventional lubricating oils for internal combustion engines must be restricted or prohibited from being included in the composition.
• the metallic detergent in order to control the content of the metal component derived from the metallic detergent in the composition to less than 0.05% by mass, the metallic detergent must also be restricted or prohibited from being included in the composition.
• the phosphorus content in the lubricating oil composition is less than 0.03% by mass on the basis of a total amount of the composition, whereas the content of the metal component derived from the metallic detergent in the lubricating oil composition is not less than 0.05% by mass and not more than 0.12% by mass on the basis of a total amount of the composition.
• the phosphorus content in the composition is less than 0.03% by mass, poisoning of active sites of a three-way catalyst can be suppressed, so that a service life of the catalyst can be extended. Therefore, the phosphorus content in the composition is preferably 0.01% by mass or less, more preferably 0.005% by mass or less and still more preferably 0.001% by mass or less.
• zinc dithiophosphate (ZnDTP) extensively used as an extremely excellent anti-wear agent in conventional lubricating oils for internal combustion engines must be restricted or prohibited from being included in the composition.
• the resulting composition can be further enhanced in detergency as required for lubricating oils for internal combustion engines.
• the content of the metal component derived from the metallic detergent in the composition is not more than 0.12% by mass or less, deposition of ashes derived from the metal component on DPF can be suppressed, so that a service life of DPF can be extended. Therefore, the content of the metal component in the composition is preferably not less than 0.05% by mass and not more than 0.10% by mass, and more preferably not less than 0.05% and not more than 0.08% by mass.
• Suitable examples of the metallic detergent from which the metal component is derived include sulfonates, phenates, salicylates and naphthenates of alkali metals (such as Na and K) and alkali earth metals (such as Ca, Mg and Ba).
• these metallic detergents preferred are Ca sulfonate, Ca phenate and Ca salicylate.
• the base number of these metallic detergents is preferably from 0 to 500 mg KOH/g, more preferably from 150 to 400 mg KOH/g and still more preferably from 200 to 350 mg KOH/g as measured by a perchloric acid method.
• the metallic detergents may be used alone or in combination of any two or more thereof.
• the content of the metallic detergent in the composition may be appropriately selected so as to adjust the content of the metal component derived from the metallic detergent in the composition to the above-specified range.
• the phosphorus content in the lubricating oil composition is not less than 0.03% by mass and not more than 0.06% by mass on the basis of a total amount of the composition, whereas the content of the metal component derived from the metallic detergent in the lubricating oil composition is less than 0.05% by mass on the basis of a total amount of the composition.
• the phosphorus content in the composition is not less than 0.03% by mass, the resulting composition can be further enhanced in wear resistance.
• the phosphorus content in the composition is not more than 0.06% by mass, poisoning of active sites of a three-way catalyst can be suppressed, so that a service life of the catalyst can be extended. Therefore, the phosphorus content in the composition is preferably not less than 0.03% by mass and not more than 0.05% by mass.
• the above phosphorus content may be controlled by adjusting an amount of the phosphorus-based anti-wear agent compounded in the composition.
• Typical examples of the phosphorus-based anti-wear agent include dithiophosphoric acid metal salts such as zinc dithiophosphate (ZnDTP) and molybdenum dithiophosphate (MoDTP); phosphoric acid esters or phosphorous acid esters (such as organic phosphoric acid esters, organic phosphorous acid esters, alkyl or aryl acid phosphates, alkyl or aryl hydrogen phosphites and amine salts of these compounds); thiophosphoric acid esters; and thiophosphorous acid esters.
• dithiophosphoric acid metal salts such as zinc dithiophosphate (ZnDTP) and molybdenum dithiophosphate (MoDTP)
• phosphoric acid esters or phosphorous acid esters such as organic phosphoric acid esters, organic phosphorous acid esters, alkyl or
• zinc dithiophosphate i.e., zinc dihydrocarbyl dithiophosphate (in which the hydrocarbyl group is an alkyl group preferably having 1 to 18 carbon atoms and more preferably 2 to 12 carbon atoms, an alkenyl group, an arylalkyl group or an alkaryl group), and more preferred are zinc dialkyl dithiophosphates containing a secondary alkyl group having 3 to 8 carbon atoms.
• the content of the metal component derived from the metallic detergent in the composition is less than 0.05% by mass, deposition of ashes derived from the metal component on DPF can be suppressed, so that a service life of DPF can be extended. Therefore, the content of the metal component in the composition is preferably 0.01% by mass or less, more preferably 0.005% by mass or less and still more preferably 0.001% by mass or less.
• the lubricating oil composition for internal combustion engines according to the present invention preferably further contains a sulfur-based anti-wear agent.
• a sulfur-based anti-wear agent include those phosphorus-free sulfur-based anti-wear agents such as sulfurized oils and fats, sulfurized fatty acids, sulfurized esters, sulfurized olefins and dihydrocarbyl polysulfides.
• sulfur-based anti-wear agents more preferred are disulfide compounds represented by the following general formula (3):
• R 1 and R 2 are each independently a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom; and A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 12 carbon atoms.
• sulfur-containing compound represented by the above general formula (3) include bis(methoxycarbonylmethyl)disulfide, bis(ethoxycarbonylmethyl)disulfide, bis(n-propoxycarbonylmethyl)disulfide, bis(isopropoxycarbonylmethyl)disulfide, bis(n-butoxycarbonylmethyl)disulfide, bis(n-octoxycarbonylmethyl)disulfide, bis(n-dodecyloxycarbonylmethyl)disulfide, bis(cyclopropoxycarbonylmethyl)disulfide, 1,1-bis(1-methoxycarbonylethyl)disulfide, 1,1-bis(1-methoxycarbonyl-n-propyl)disulfide, 1,1-bis(1 - methoxycarbonyl-n-butyl)disulfide, 1,1-bis(1-methoxycarbonyl-n-hexyl)d
• the content of the sulfur-based anti-wear agent in the composition is preferably from 0.05 to 5% by mass andmore preferably from 0.1 to 3% bymass on the basis of a total amount of the composition.
• the content of the sulfur-based anti-wear agent in the composition is 0.05% by mass or more, the resulting composition can exhibit a sufficient wear resistance.
• the content of the sulfur-based anti-wear agent in the composition is 5% by mass or less, the resulting composition is free from occurrence of corrosion.
• the lubricating oil composition according to the present invention may further contain other additives used in conventionally known lubricating oil compositions such as lubricating oils for internal combustion engines unless they give any adverse influence on the conditions of the phosphorus content and the content of the metal component as required in the present invention.
• the other additives include the other friction reducing agent, a viscosity index improver, a pour point depressant, an antioxidant and a rust inhibitor.
• the other friction reducing agent include ash-free friction reducing agents such as fatty acid ester-based compounds, fatty amine-based compounds and higher alcohol-based compounds.
• viscosity index improver examples include so-called non-dispersed type viscosity index improvers such as copolymers of various methacrylic acid esters or an optional combination of the methacrylic acid esters and hydrogenated products thereof, and so-called dispersed type viscosity index improvers such as copolymers obtained by further copolymerizing various nitrogen compound-containing methacrylic acid esters with the above compounds.
• viscosity index improver examples include non-dispersed type or dispersed type ethylene- ⁇ -olefin copolymers (in which the ⁇ -olefin include, for example, propylene, 1-butene, 1-pentene, etc.) and hydrogenated products thereof, polyisobutylene and hydrogenated products thereof, hydrogenated styrene-diene copolymers, styrene-maleic anhydride ester copolymers and polyalkyl styrenes.
• the molecular weight (number-average molecular weight) of these viscosity index improvers is, for example, as follows.
• the number-average molecular weight of the dispersed type or non-dispersed type polymethacrylates is from 5000 to 1000000 and preferably from 100000 to 800000.
• the number-average molecular weight of the polyisobutylene and hydrogenated products thereof is from 800 to 5000.
• the number-average molecular weight of the ethylene- ⁇ -olefin copolymers and hydrogenated products thereof is from 800 to 300000 and preferably from 10000 to 200000.
• antioxidants examples include phenol-based antioxidants and amine-based antioxidants.
• phenol-based antioxidants include 4,4′-methylene bis(2,6-d-t-butyl phenol); 4,4′-bis(2,6-di-t-butyl phenol); 4,4′-bis(2-methyl-6-t-butyl phenol) ; 2,2′-methylene bis(4-ethyl-6-t-butyl phenol); 2,2′-methylene bis(4-methyl-6-t-butyl phenol); 4,4′-butylidene bis(3-methyl-6-t-butyl phenol); 4,4′-isopropylidene bis(2,6-di-t-butylphenol);2,2′-methylenebis(4-methyl-6-nonyl phenol); 2,2′-isobutylidene bis(4,6-dimethyl phenol); 2,2′-methylene bis(4-methyl-6-cyclohexyl phenol); 2,6-di-
• amine-based antioxidants examples include monoalkyl diphenyl amine-based antioxidants such as monooctyl diphenyl amine and monononyl diphenyl amine; dialkyl diphenyl amine-based antioxidants such as 4,4′-dibutyl diphenyl amine, 4,4′-dipentyl diphenyl amine, 4,4′-dihexyl diphenyl amine, 4,4′-diheptyl diphenyl amine, 4,4′-dioctyl diphenyl amine and 4,4′-dinonyl diphenyl amine; polyalkyl diphenyl amine-based antioxidants such as tetrabutyl diphenyl amine, tetrahexyl diphenyl amine, tetraoctyl diphenyl amine and tetranonyl diphenyl amine; and naphtyl amine-based antioxidants.
• naphtyl amine-based antioxidants include ⁇ -naphtyl amine; phenyl- ⁇ -naphtyl amine; and alkyl-substituted phenyl- ⁇ -naphtyl amines such as butyl phenyl-a-naphtyl amine, pentyl phenyl- ⁇ -naphtyl amine, hexyl phenyl- ⁇ -naphtyl amine, heptyl phenyl- ⁇ -naphtyl amine, octyl phenyl- ⁇ -naphtyl amine and nonyl phenyl- ⁇ -naphtyl amine.
• these amine-based antioxidants preferred are dialkyl diphenyl amine-based antioxidants and naphtyl amine-based antioxidants.
• antioxidants may be used alone or in combination of any two or more thereof.
• one or more kinds of the phenol-based antioxidants are used in combination with one or more kinds of the amine-based antioxidants.
• rust inhibitor examples include alkyl benzene sulfonates, dinonyl naphthalene sulfonate, alkenyl succinic acid esters and polyhydric alcohol esters.
• the amounts of the above other additives compounded in the composition may be appropriately selected from an ordinary practical range.
• the lubricating oil composition having such a performance as aimed by the present invention can be obtained by compounding the various additives mentioned above in a base oil for lubricants (hereinafter occasionally referred to merely as a “base oil”).
• the base oil used in the present invention is not particularly limited, and may be appropriately selected from conventionally known mineral base oils (hereinafter also referred to merely as “mineral oils”) and conventionally known synthetic base oils (hereinafter also referred to merely as “synthetic oils”).
• mineral oils examples include distilled oils obtained by subjecting a paraffin base crude oil, an intermediate base crude oil or a naphthene base crude oil to atmospheric distillation, or subjecting a residue oil obtained from the atmospheric distillation to distillation under reduced pressure, and refined oils obtained by subjecting these oils to ordinary purification treatments.
• refined oils include solvent-refined oils, hydrogenation refined oils, hydrocracked oils, dewaxed oils and clay-treated oils as well as isomerized oils of waxes (such as slack wax).
• synthetic oils examples include poly- ⁇ -olefins such as ⁇ -olefin oligomers having 8 to 14 carbon atoms, polybutene, polyol esters and alkyl benzenes.
• the above mineral oils may be used alone or in combination of any two or more thereof.
• the above synthetic oils may be used alone or in combination of any two or more thereof.
• one or more kinds of the mineral oils may be used in combination with one or more kinds of the synthetic oils.
• the content of the base oil in the composition is preferably 70% by mass or more, and more preferably 80% by mass or more.
• the kinematic viscosity of the base oil as measured at 100° C. is preferably in the range of from 1.5 to 50 mm 2 /s, more preferably from 3 to 30 mm 2 /s and still more preferably from 3 to 15 mm 2 /s.
• the kinematic viscosity of the base oil as measured at 100° C. is 1.5 mm 2 /s or more, the resulting lubricating oil composition hardly suffers from evaporation loss.
• the kinematic viscosity of the base oil as measured at 100° C. is 50 mm 2 /s or less, power loss owing to a viscosity resistance of the resulting lubricating oil composition can be suppressed, so that the composition can exhibit a good effect of improving a fuel consumption.
• the viscosity index of the base oil is preferably 80 or more, more preferably 90 or more, and still more preferably 100 or more.
• the base oil having a viscosity index of 80 or more has a less change in viscosity depending upon temperature and therefore can exhibit a stable lubricating performance.
• the base oil preferably has a sulfur content of 50 ppm by mass or less as measured according to JIS K 2541.
• the sulfur content of the base oil is 50 ppm by mass or less, the resulting lubricating oil composition can exhibit an effect of enhancing a wear resistance of a low-friction slide material.
• the sulfur content of the base oil is more preferably 30 ppm by mass or less and still more preferably 20 ppm by mass or less.
• the base oil preferably has a % C A value of 3.0 or less as measured by ring analysis from the viewpoint of a good stability of the resulting lubricating oil composition.
• the % C A value according to ring analysis as used herein means a proportion (percentage) of an aromatic component in the base oil which is calculated by a ring analysis n-d-M method.
• the % C A value of the base oil is 3.0 or less, the resulting lubricating oil composition can exhibit a good oxidation stability.
• the % C A value of the base oil is more preferably 1.0 or less and more preferably 0.5 or less.
• lubricating oil composition for internal combustion engines (hereinafter also referred to merely as a “lubricating oil composition”) were measured by the following methods.
• SRV friction tester reciprocating type friction tester
• the lubricating oil compositions having formulations as shown in Tables 1 and 2 were prepared and subjected to measurement of a wear resistance. The results are shown in Tables 1 and 2.
• the respective components used for preparing the lubricating oil compositions are as follows.
• the lubricating oil compositions capable of satisfying the formula (I) according to the present invention were excellent in wear resistance for aluminum materials (Examples A1 to A10).
• the lubricating oil compositions obtained in Examples A4 to A8 which were capable of satisfying the formula (II) were further excellent in wear resistance for aluminum materials.
• the lubricating oil compositions according to the present invention (Examples A1 to A10) exhibited a good wear resistance even when they had no P content.
• the lubricating oil compositions according to the present invention were extremely reduced in both of P content and content of the metal component derived from the metallic detergent, and therefore were extremely excellent in effects of preventing poisoning of a three-way catalyst and suppressing deterioration in service life of DPF.
• the lubricating oil compositions having formulations as shown in Tables 3 and 4 were prepared and subjected to measurement of a wear resistance. The results are shown in Tables 3 and 4.
• the lubricating oil compositions capable of satisfying the formula (I) according to the present invention were excellent in wear resistance for aluminum materials (Examples B1 to B9).
• the lubricating oil compositions obtained in Examples B5 to B8 which were capable of satisfying the formula (II) were further excellent in wear resistance for aluminum materials.
• the lubricating oil compositions according to the present invention (Examples B1 to B9) exhibited a good wear resistance even when they had substantially no P content.
• the lubricating oil compositions according to the present invention exhibited an extremely reduced P content, and therefore were extremely excellent in effect of preventing poisoning of a three-way catalyst.
• the content of the metal component derived from the metallic detergent in the lubricating oil compositions according to the present invention was 0.05% by mass or more, so that the compositions exhibited a very good detergency owing to inclusion of an adequate amount of the metallic detergent therein.
• the content of the metal component derived from the metallic detergent in the lubricating oil compositions according to the present invention was 0.12% by mass or less, so that the compositions also exhibited a good effect of suppressing deterioration in service life of DPF.
• the lubricating oil compositions having formulations as shown in Tables 5 and 6 were prepared and subjected to measurement of a wear resistance. The results are shown in Tables 5 and 6.
• the lubricating oil compositions capable of satisfying the formula (I) according to the present invention were excellent in wear resistance for aluminum materials (Examples C1 to C10).
• the lubricating oil compositions obtained in Examples C5 to C8 which were capable of satisfying the formula (II) were further excellent in wear resistance for aluminum materials.
• the lubricating oil compositions according to the present invention were still more excellent in wear resistance since the P content therein was 0.03% by mass or more.
• the P content in the lubricating oil compositions according to the present invention was 0.06% by mass or less, so that the compositions exhibited a good effect of preventing poisoning of a three-way catalyst.
• the content of the metal component in the lubricating oil compositions according to the present invention was less than 0.05% by mass, so that the compositions were extremely excellent in effect of suppressing deterioration in service life of DPF.
• the lubricating oil composition for internal combustion engines according to the present invention is excellent in wear resistance for aluminum materials.
• the lubricating oil composition according to the present invention can be usefully used as a lubricating oil composition for internal combustion engines which is capable of reducing an adverse influence on an exhaust gas post-treatment device for internal combustion engines which is formed of an aluminum material.

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

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• 2012
  • 2012-08-03 WO PCT/JP2012/069911 patent/WO2013018907A1/ja active Application Filing
  • 2012-08-03 US US14/236,190 patent/US20140194329A1/en not_active Abandoned
  • 2012-08-03 CN CN201280038401.5A patent/CN103717720A/zh active Pending
  • 2012-08-03 IN IN785CHN2014 patent/IN2014CN00785A/en unknown
  • 2012-08-03 KR KR1020147002641A patent/KR20140058531A/ko not_active Withdrawn
  • 2012-08-03 CA CA2843554A patent/CA2843554A1/en not_active Abandoned
  • 2012-08-03 EP EP12820418.7A patent/EP2740783A4/en not_active Withdrawn

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