EP2610331B1 - Schmiermittelzusammensetzung für verbrennungsmotoren - Google Patents

Schmiermittelzusammensetzung für verbrennungsmotoren Download PDF

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Publication number
EP2610331B1
EP2610331B1 EP11819862.1A EP11819862A EP2610331B1 EP 2610331 B1 EP2610331 B1 EP 2610331B1 EP 11819862 A EP11819862 A EP 11819862A EP 2610331 B1 EP2610331 B1 EP 2610331B1
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EP
European Patent Office
Prior art keywords
lubricating oil
internal combustion
oil composition
combustion engine
group
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EP11819862.1A
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English (en)
French (fr)
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EP2610331A4 (de
EP2610331A1 (de
Inventor
Kazuhiro Umehara
Kenji Yamamoto
Masaki Maruyama
Yasushi Naito
Satoru Yoshida
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Adeka Corp
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/16—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • C—CHEMISTRY; METALLURGY
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/28—Carboxylic acids or their salts having only one carboxyl group bound to a carbon atom of a six-membered aromatic ring
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    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/30—Carboxylic acids or their salts having more than one carboxyl group bound to a carbon atom of a six-membered aromatic ring
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    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/40—Esters containing free hydroxy or carboxyl groups
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    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C10M105/44—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • 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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    • 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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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
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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
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    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • 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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    • 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
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    • C10M2215/064—Di- and triaryl amines
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    • 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
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    • 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
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    • C10M2223/045—Metal containing thio derivatives
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    • C10N2020/02—Viscosity; Viscosity index
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    • C10N2030/04—Detergent property or dispersant property
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    • C10N2030/08—Resistance to extreme temperature
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    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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    • C10N2030/54—Fuel economy
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
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    • C10N2040/252—Diesel engines
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    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to a lubricating oil composition for an internal combustion engine, and more specifically, to a lubricating oil composition for an internal combustion engine having excellent fuel-saving property and high-temperature deposit-preventing performance.
  • a lubricating oil for internal combustion engines of automobiles or the like plays roles such as the lubrication and cooling of the inside of the engine, and the cleaning and dispersion of combustion products .
  • a fuel-saving-type lubricating oil for an internal combustion engine obtained by providing a lubricating oil for an internal combustion engine with a function of improving fuel efficiency has been studied and used.
  • Fuel-saving-type lubricating oils for internal combustion engines reduce friction occurring in an internal combustion engine to improve the fuel efficiency of the engine.
  • an organic molybdenum-based friction modifier such as a molybdenum dithiocarbamate is generally blended as an additive (friction modifier) for reducing the friction.
  • lubricants for internal combustion engines blended with organic molybdenum-based friction modifiers are apt to generate high-temperature deposits because of poor oxidation stability under high temperatures.
  • recent lean-burn engines, direct-injection engines, or the like have higher efficiency than conventional engines, and their combustion temperatures tend to increase. Accordingly, problems due to generation of high-temperature deposits have become serious.
  • Patent Document 1 discloses a multigrade engine oil composition for an engine with a turbocharger, the composition being characterized by using a mineral oil and/or a synthetic oil having a kinematic viscosity of 1.5 to 13 cSt (100°C) as a base oil, and containing, as essential components, 3 to 40 mass% of (A) a mineral oil and/or a synthetic oil having a kinematic viscosity of 16 to 45 cSt (100°C) and 0.5 to 15 mass% of (B) a viscosity index improver.
  • Patent Document 2 discloses a lubricating oil composition for an internal combustion engine characterized by using, as a base oil, a lubricating oil component that has a kinematic viscosity at 100°C of 2 cSt to 13 cSt and contains 1 mass% or more of a heavy component having a boiling point of 480°C or more in a boiling point range measured by gas chromatograph distillation with reference to the total mass of the lubricating oil base oil.
  • an organic molybdenum-based compound can be used as a friction modifier.
  • JP-A 2001 131570 A describes lubricating compositions with friction reduction effect and fuel efficiency, based on a mixture of at least two base oils with different kinematic viscosity, and further comprising molybdenum dithiocarbamate and Zn-dithiophosphate.
  • JP-A-2008 303241 discloses lubricating compositions with deposit performance at high-temperature, low-friction characteristics and low fuel consumption, based on a mineral and/or synthetic base oil, an alkaline earth metal-detergent, and specific amounts of ZnDTP and MoDTC.
  • a problem to be solved by the present invention is to provide a lubricating oil composition for an internal combustion engine having high-temperature deposit-preventing performance while maintaining excellent fuel-saving property.
  • the present inventors have made extensive studies to find that excellent fuel-saving performance and high-temperature deposit-preventing performance can be imparted by blending a lubricating oil composition for an internal combustion engine with an organic molybdenum compound and a plurality of base oils each having a specific viscosity. Thus, the inventors have reached the present invention.
  • a lubricating oil composition for an internal combustion engine includes: an organic molybdenum compound as a component (A) ; a base oil having a kinematic viscosity at 100 °C of 25 mm 2 /s or more as a component (B) ; and a base oil having a kinematic viscosity at 100°C of less than 12.5 mm 2 /s as a component (C), in which the composition has a kinematic viscosity at 100°C of 5 mm 2 /s to 12.5 mm 2 /s and a phosphorus content of 800 ppm or less.
  • An effect of the present invention resides in the provision of the lubricating oil composition for an internal combustion engine having high-temperature deposit-preventing performance while maintaining excellent fuel-saving property.
  • a lubricating oil composition for an internal combustion engine of the present invention contains an organic molybdenum compound as a component (A).
  • Any one of the known organic molybdenum compounds can be used as the organic molybdenum compound, and examples thereof include: a molybdenum dithiocarbamate; a molybdenum dithiophosphate; a molybdenum amine compound listed in JP 05-62639 B or the like [an oil-soluble molybdenum compound obtained by reacting one or more kinds of hexavalent molybdenum compounds selected from molybdenum trioxide, and molybdic acid and an alkali salt thereof, and an amino compound represented by R 1 R 2 R 3 N (R 1 , R 2 , and R 3 each represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms and may be identical to or different from one another, and the total number of carbon atoms of R 1 , R 2 , and R 3 is 4 or more) with
  • a molybdenum dithiocarbamate represented by the following general formula (1) is preferred because of its large friction-reducing effect.
  • the organic molybdenum compound may be one kind or a mixture of two or more kinds.
  • the amount of the compound to be added to the lubricating oil composition for an internal combustion engine of the present invention is as indicated in appended claim 1. When the addition amount is small, there are cases where a friction-reducing effect is not obtained. In addition, when the addition amount is excessively large, high-temperature deposits outstripping the effect of the high-temperature deposit-preventing performance of the lubricating oil composition for an internal combustion engine of the present invention may be generated.
  • the compound is added at a molybdenum content of 200 to 2,000 ppm, more preferably 200 to 1,500 ppm, still more preferably 300 to 1,000 ppm with respect to the total amount of the lubricating oil composition for an internal combustion engine of the present invention.
  • the component (B) used in the present invention is a base oil having a kinematic viscosity at 100°C of 25 mm 2 /s or more, and a mineral oil-based base oil, a synthetic base oils, or a mixed oil thereof can be used as such base oil.
  • a paraffin-based mineral oil and a naphthene-based mineral oil can be given as examples of the mineral oil-based base oil, and a solvent-refined oil, oil obtained by a hydrogenation treatment, wax-isomerized oil, or the like of any such oil may be used.
  • a poly- ⁇ -olefin, a polyisobutylene (polybutene), a diester, a polyol ester, or a polyphenyl ether can be used as the synthetic base oil.
  • a paraffin-based mineral oil such as a bright stock and a high-viscosity poly- ⁇ -olefin are preferred.
  • the kinematic viscosity at 100°C of the component must be 25 mm 2 /s or more, and is preferably 25 to 100 mm 2 /s, more preferably 25 to 80 mm 2 /s, still more preferably 30 to 60 mm 2 /s.
  • the kinematic viscosity at 100°C is less than 25 mm 2 /s, the high-temperature deposit-preventing performance is not sufficiently exerted.
  • the viscosity is excessively high, there are problems such as cases where it may be difficult to handle the component or it takes a long time to uniformly blend the component. Accordingly, the kinematic viscosity is preferably 100 mm 2 /s or less.
  • the blending amount of the component (B) is s indicated in appended claim 1.
  • the blending amount is excessively small, there are cases where the effect of the high-temperature deposit-preventing performance may not be exerted.
  • the blending amount is excessively large, it may be difficult to set the kinematic viscosity at 100°C of the lubricating oil composition for an internal combustion engine of the present invention to 12.5 mm 2 /s or less, or its low-temperature viscosity may increase to reduce its fuel-saving effect.
  • the blending amount of the component (B) is 1 to 30 mass%, more preferably 3 to 25 mass%, still more preferably 5 to 20 mass% with respect to the total amount of the lubricating oil composition for an internal combustion engine of the present invention.
  • the component (C) used in the present invention is a base oil having a kinematic viscosity at 100°C of less than 12.5 mm 2 /s.
  • a mineral oil-based base oil, a synthetic base oil, or a mixed oil thereof can be used as such base oil, and examples of such base oil include: mineral oil-based base oils such as a paraffin-based mineral oil and a naphthene-based mineral oil, oils obtained by subjecting these mineral oils to a solvent refining treatment, a hydrogenation treatment, and a wax isomerization treatment, and a mineral oil obtained by combining two or more of these treatments; and synthetic oils such as poly- ⁇ -olefins and polyisobutylenes.
  • the kinematic viscosity of the component (C) is 12. 5 mm 2 /s or more, a lubricating oil composition having a kinematic viscosity in the range specified in the present invention cannot be produced.
  • the kinematic viscosity of the component (C) is less than 12.5 mm 2 /s, in the case where the component is a base oil having an excessively high viscosity, the amount of the high-viscosity base oil that can be added is reduced, and hence it may be unable to efficiently alleviate the generation of high-temperature deposits or the low-temperature viscosity of the lubricating oil composition for an internal combustion engine of the present invention may increase to reduce its fuel-saving effect.
  • the kinematic viscosity at 100°C of the component (C) is preferably 1 to 11 mm 2 /s, more preferably 2 to 8 mm 2 /s, still more preferably 2 to 5 mm 2 /s.
  • the viscosity index of the component (C) is preferably 100 or more, more preferably 110 or more, still more preferably 120 or more from the viewpoint of improving fuel-saving properties.
  • the viscosity index of the low-viscosity base oil is less than 100, the low-temperature viscosity of the lubricating oil composition for an internal combustion engine as the end product increases, with the result that the fuel-saving effect is not obtained in some cases.
  • the component (C) has to be blended in such an amount that the lubricating oil composition for an internal combustion engine of the present invention blended with any other additive or the like has a kinematic viscosity at 100°C of 5 mm 2 /s to 12.5 mm 2 /s. Specifically, the component has only to be blended in an amount of 50 to 95 mass%, preferably 60 to 85 mass% with respect to the total amount of the lubricating oil composition of the present invention.
  • the lubricating oil composition for an internal combustion engine of the present invention containing the components (A) to (C) must have a phosphorus content of 800 ppm to 500 ppm.
  • phosphorus-based additive examples include metal-containing additives such as molybdenum dithiophosphate and zinc dithiophosphate; extreme-pressure agents such as monooctyl phosphate, dioctyl phosphate, monooleyl phosphate, dioleyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, tributyl phosphite, tricresyl phosphite, and a thiophosphoric acid ester; and detergents such as calcium phosphate, magnesium phosphate, and barium phosphate.
  • metal-containing additives such as molybdenum dithiophosphate and zinc dithiophosphate
  • extreme-pressure agents such as monooctyl phosphate, dioctyl phosphate, monooleyl phosphate, dioleyl phosphate, tributyl phosphate, tripheny
  • the addition amount thereof must be 800 ppm or less in terms of a phosphorus content. As long as the addition amount is 800 ppm or less, the amount of high-temperature deposits generated is nearly immune to the phosphorus concentration . However, when the phosphorus concentration exceeds 800 ppm, the amount of high-temperature deposits generated abruptly increases. However, when the phosphorus concentration is excessively low, the lubricating oil for an internal combustion engine may be poor in wear resistance or oxidation-preventing property. Accordingly, phosphorus is present in a certain amount or more. The phosphorus content may be 300 to 800 ppm. According to the invention is 500 to 800 ppm. Further, the phosphorus compound most suitable for the addition is a zinc dithiophosphate excellent in wear resistance and oxidation-preventing property.
  • the lubricating oil composition for an internal combustion engine of the present invention has a kinematic viscosity at 100°C of 5 mm 2 /s to 12.5 mm 2 /s.
  • a kinematic viscosity at 100°C of 5 mm 2 /s to 12.5 mm 2 /s.
  • the kinematic viscosity is less than 5 mm 2 /s, there is a possibility that oil film does not sufficiently form and hence wear occurs at sliding surfaces.
  • the kinematic viscosity is more than 12.5 mm 2 /s, the following problem arises. The oil film becomes so thick that friction loss increases to impair fuel-saving performance.
  • high-temperature deposit refers to insoluble matter resulting from the lubricating oil composition for an internal combustion engine, the insoluble matter being produced at high temperatures of 300°C or 400 °C or more.
  • the adhesion and deposition of such high-temperature deposits to, for example, the inside of an engine or the bearings of a supercharger may induce a reduction in performance of the engine or the supercharger, or trouble in the engine or the supercharger.
  • the major feature of the lubricating oil composition for an internal combustion engine of the present invention is that the amount of high-temperature deposits generated is small.
  • the composition may be evaluated by any one of the known tests for observing high-temperature deposits, the composition is preferably evaluated by a TEOST33C test (ASTM D6335) adopted by the International Lubricant Standardization and Approval Committee (ILSAC) because an additionally strict evaluation can be performed.
  • the amount is preferably 40 mg or less, more preferably 30 mg or less in the TEOST33C test because nearly no reduction in performance of an engine or in performance of a supercharger is observed at the time of practical use.
  • One or more kinds of additives such as viscosity index improvers, pour point depressants, extreme-pressure agents, oiliness improvers, antioxidants, metal-based detergents, ashless dispersants, metal deactivators, rust inhibitors, and anti-foaming agents are preferably added to the lubricating oil composition for an internal combustion engine of the present invention as long as the effects of the present invention are not impaired. Further, when any such additive is blended, particular attention needs to be paid so that the phosphorus content with respect to the total amount of the lubricating oil composition for an internal combustion engine will be 800 ppm to 500 ppm.
  • viscosity index improvers examples include poly(C1 to C18)alkyl methacrylates, (C1 to C18)alkyl crylate/(C1 to C18)alkyl methacrylate copolymers, diethylaminoethyl methacrylate/(C1 to C18)alkyl methacrylate copolymers, ethylene/(C1 to C18)alkyl methacrylate copolymers, polyisobutylenes, polyalkylstyrenes, ethylene/propylene copolymers, styrene/maleic acid ester copolymers, and styrene/isoprene hydrogenated copolymers.
  • a dispersion-type or multi-functional viscosity index improver to which dispersing performance has been imparted may be used. Its weight-average molecular weight is about 10,000 to 1,500,000, preferably about 30,000 to 1,000, 000.
  • Such viscosity index improver is blended in an amount of preferably 0.1 to 20 mass%, more preferably 0.3 to 15 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • pour point depressants examples include polyalkyl methacrylates, polyalkyl acrylates, polyalkylstyrenes, and polyvinyl acetates. Its weight-average molecular weight is about 1,000 to 100,000, preferably about 3,000 to 80,000. Such pour point depressant is blended in an amount of preferably 0.005 to 3 mass%, more preferably 0.01 to 2 mass%, with respect to the lubricating oil composition for an internal combustion engine.
  • extreme-pressure agents include: sulfur-based additives such as sulfurized oils and fats, olefin polysulfides, and dibenzyl sulfides; phosphorus-based compounds such as monooctyl phosphate, tributylphosphate, triphenylphosphite, tributyl phosphite, and thiophosphoric acid esters; and organic metal compounds such as metal salts of thiophosphoric acid, metal salts of thiocarbamic acid, and metal salts of an acidic phosphoric acid ester.
  • sulfur-based additives such as sulfurized oils and fats, olefin polysulfides, and dibenzyl sulfides
  • phosphorus-based compounds such as monooctyl phosphate, tributylphosphate, triphenylphosphite, tributyl phosphite, and thiophosphoric acid esters
  • organic metal compounds such as metal salts of thio
  • oiliness improvers include: higher alcohols such as oleyl alcohol and stearyl alcohol; fatty acids such as oleic acid and stearic acid; esters such as oleyl glycerine ester, stearyl glycerine ester, and lauryl glycerine ester; amides such as lauryl amide, oleyl amide, and stearyl amide; amines such as laurylamine, oleylamine, and stearylamine; and ethers such as lauryl glycerine ether and oleyl glycerine ether.
  • Such oiliness improver is blended in an amount of preferably 0.1 to 5 mass%, more preferably 0.2 to 3 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • antioxidants include: phenol-based antioxidants such as 2,6-ditertiary butylphenol (hereinafter, tertiary butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylene bis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 4,4'-bis(2-methyl-6-t-butylphenol), 2,2'-methylene bis(4-methyl-6-t-butylphenol), 2,2'-methylene bis(4-ethyl-6-t-butylphenol), 4,4'-butylidene bis(3-methyl-6-t-butylphenol), 4,4'-isopropylidene bis(
  • metal-based detergents examples include sulfonates, phenates, salicylates, and phosphates of calcium, magnesium, and barium, and perbasic salts thereof. Of those, perbasic salts are preferred. Of the perbasic salts, a perbasic salt having a total basic number (TBN) of 30 to 500 mgKOH/g is more preferred. A salicylate-based detergent free of phosphorus and sulfur atoms is still more preferred. Such metal-based detergent is blended in an amount of preferably 0.5 to 10 mass%, more preferably 1 to 8 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • ashless dispersants examples include succinimide, a succinic acid ester, and benzylamine to each of which an alkyl group or an alkenyl group has been added and each of which has a weight-average molecular weight of about 500 to 3,000, and boron-denatured products thereof.
  • Such ashless dispersant is blended in an amount of preferably 0.5 to 10 mass%, more preferably 1 to 8 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • metal deactivators examples include benzotriazole, benzimidazole, benzothiazole, and a tetraalkylthiuram disulfide. Such metal deactivator is blended in an amount of preferably 0.01 to 3 mass%, more preferably 0.02 to 2 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • rust inhibitors include sodium nitrite, oxidized paraffin wax calcium salts, oxidized paraffin wax magnesium salts, beef tallow fatty acid alkali metal salts, alkaline earth metal salts, or amine salts, alkenyl succinic acids or alkenyl succinic acid half esters (the molecular weight of the alkenyl group is about 100 to 300), sorbitan monoester, nonylphenol ethoxylate, and calcium salt of a lanolin fatty acid.
  • Such rust inhibitor is blended in an amount of preferably 0.01 to 3 mass%, more preferably 0.02 to 2 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • anti-foaming agents examples include polydimethylsilicone, trifluoropropylmethylsilicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy/propoxylate, fatty acid ethoxy/propoxylate, and sorbitan partial fatty acid ester.
  • Such anti-foaming agent is blended in an amount of preferably 0.001 to 0.1 mass%, more preferably 0.001 to 0.01 mass% with respect to the lubricating oil composition for an internal combustion engine.
  • the lubricating oil composition for an internal combustion engine of the present invention can be used as a lubricating oil for any internal combustion engine as long as the internal combustion engine is, for example, a gasoline engine, adieselengine, and a natural gas engine (liquefied petroleum gas engine) and among these the composition can be favorably used as an engine oil for gasoline engines.
  • the internal combustion engine is, for example, a gasoline engine, adieselengine, and a natural gas engine (liquefied petroleum gas engine) and among these the composition can be favorably used as an engine oil for gasoline engines.
  • Lubricating oil compositions for internal combustion engines used in tests were produced in accordance with the recipes shown in Table 1 and Table 2 below, and were then subjected to the TEOST33C test and a fuel-saving property test by the following methods.
  • Table 1 and Table 2 show the results.
  • Table 3 shows a base oil used in blending and its properties.
  • FIG. 1 is a schematic view of the TEOST33C tester.
  • the specific test method is as described below. While a rod (metal rod) (2) in a case (1) of the apparatus illustrated in FIG. 1 was heated and cooled so that its temperature was as shown in FIG. 2 , a certain amount of a test oil was made to flow from a reaction chamber (4) storing the test oil into the rod (2) in the case (1) by a pump (3). The step is defined as 1 cycle and the cycle was repeated 12 times.
  • the rod was taken out, and then the mass of deposits adhering thereto and the mass of deposits in the test oil obtained by filtering the total amount of the test oil through a filter were measured.
  • the total of the masses was defined as a high-temperature deposit amount. Further, certain amounts of air containing moisture and a nitrogen monoxide gas were blown into the test oil in the reaction chamber (4). Further, air bubbled in 30 ml of water in a 50-ml flask was used as the air containing moisture.
  • Test cycle 12 cycles Testing time: 9.5 minutes per cycle (total testing time: 114 minutes) Amount of test oil: 106 ml Catalyst: iron naphthenate (added to the test oil in an amount of 100 ppm in terms of iron content) Pump rate: 0.49 ml/min Flow rate of N 2 O gas: 3.5 ml/min Flow rate of air: 3.5 ml/min
  • Viscosity index improver polymethacrylate-based viscosity index improver
  • Detergent calcium salicylate (TBN280)
  • Dispersant polyalkenyl succinimide
  • Antioxidant mixture of benzenepropanoic acid 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxyoctyl ester and dioctyldiphenylamine (mass ratio: 1/1)
  • Zinc dithiophosphate zinc dialkyldithiophosphate whose alkyl group is linear and a mixture of alkyl groups having 4 to 6 carbon atoms (phosphorus content: 8.67%)
  • Molybdenum dithiocarbamate molybdenum dithiocarbamate of the general formula (1) in which R 1 to R 4 each represent a mixture of groups having 8 or 13 carbon atoms, X 1 and X 2 each represent an oxygen atom, and X 3 and

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Claims (4)

  1. Schmierölzusammensetzung für einen Verbrennungsmotor umfassend:
    - 200 bis 2000 ppm, in Bezug auf den Molybdängehalt, hinsichtlich der Gesamtmenge der Schmierölzusammensetzung, einer organischen Molybdänverbindung als Bestandteil (A);
    - 1 bis 30 Massen-%, hinsichtlich der Gesamtmenge der Schmierölzusammensetzung, eines Basisöls mit einer kinematischen Viskosität bei 100°C von 25 mm2/s oder mehr als Bestandteil (B); und
    - 50 bis 95 Massen-%, hinsichtlich der Gesamtmenge der Schmierölzusammensetzung, eines Basisöls mit einer kinematischen Viskosität bei 100°C von weniger als 12,5 mm2/s als Bestandteil (C),
    wobei die Zusammensetzung bei 100°C eine kinematische Viskosität von 5 mm2/s bis 12,5 mm2/s und einen Phosphorgehalt von 500 bis 800 ppm hinsichtlich der Gesamtmenge der Schmierölzusammensetzung hat.
  2. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, wobei der Bestandteil (A) eine Verbindung, die durch die folgende allgemeine Formel (1) dargestellt wird, umfasst:
    Figure imgb0006
     wobei R1 bis R4 jeweils eine lineare oder verzweigte Alkylgruppe oder Alkenylgruppe mit 4 bis 18 Kohlenstoffatomen darstellen, und X1 bis X4 jeweils ein Sauerstoffatom oder ein Schwefelatom darstellen.
  3. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1 oder 2, wobei die Schmierölzusammensetzung für einen Verbrennungsmotor weiterhin eine oder mehrere Arten von Additiven ausgewählt aus der Gruppe bestehend aus einem Viskositätsindexverbesserer, einem Pourpointerniedriger, einem Hochdruckzusatz, einem Öligkeitsverbesserer, einem Antioxidationsmittel, einem Metall-basierten Detergens, einem aschefreien Dispergiermittel, einem Metal-Deaktivierer, einem Rostinhibitor und einem Antischaummittel umfasst.
  4. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 3, wobei die Schmierölzusammensetzung für einen Verbrennungsmotor 500 bis 800 ppm, hinsichtlich des Phosphorgehalts, Zinkdithiophosphat als Hochdruckzusatz in Bezug auf die Gesamtmenge davon enthält.
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US20130310289A1 (en) 2013-11-21
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EP2610331A1 (de) 2013-07-03
CN103068955B (zh) 2016-04-06
KR20130108532A (ko) 2013-10-04
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