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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
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  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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  • 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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  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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  • 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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  • C10M2207/00—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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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
  • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy compounds
  • C10M2207/2835—Esters of polyhydroxy compounds used as base material
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
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  • 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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  • 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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  • 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
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  • 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
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  • 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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  • 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
  • C10N2020/02—Viscosity; Viscosity index
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  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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  • C10N2020/04—Molecular weight; Molecular weight distribution
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
  • C10N2030/041—Soot induced viscosity control
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/45—Ash-less or low ash content
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  • C10N2030/74—Noack Volatility
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/78—Fuel contamination
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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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  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines

Definitions

• the present invention relates to a lubricating oil composition to be used in an internal combustion engine that uses a fuel originating from natural fat and oil.
• Non-Patent Document 1 Koji YAMANE, BIODIESEL—From Deep Fryer to Fuel Tank, (Tokyo-Tosho-Shuppankai, May of 2006)
• An effective solution is to mount such an exhaust purifying device as a diesel particulate filter (DPF) or an exhaust purifying catalyst (oxidization or reduction catalyst) on an automobile.
• soot generated in the diesel engine adheres to the DPF to be removed by oxidization and combustion.
• lubricating oil sufficiently adapted for use with biofuel has not been provided yet.
• content in the lubricant oil such as metal content, phosphorus content or sulfur content is simply decreased, lubricity thereof may be damaged despite the intentions.
• An object of the invention is to provide a lubricating oil composition that is excellent in lubricity and engine-parts detergency even when biofuel or biofuel-mixed fuel is employed in an internal combustion engine such as a diesel engine.
• lubricating oil compositions as follows are provided:
• a lubricating oil composition used in an internal combustion engine the internal combustion engine using a fuel that contains at least one fat and oil selected from a group consisting of natural fat and oil, hydrotreated natural fat and oil, transesterified natural fat and oil and hydrotreated transesterified natural fat and oil, in which a polyol ester having a kinematic viscosity in the range of 3 to 8 mm 2 /s at 100 degrees C. and/or a polybasic acid ester having a kinematic viscosity in the range of 3 to 8 mm 2 /s at 100 degrees C.
• the above-described lubricating oil composition in which a boron derivative of polybutenyl succcinimide compound including a polybutenyl group that has a number average molecular weight of 500 to 3500 and possessing a mass ratio (B/N) between boron (B) and nitrogen (N) of 0.5 or more, and an alkaline earth metal detergent are mixed; (3) the above-described lubricating oil composition, in which a sulfated ash content is 1.1 mass % or less; (4) the above-described lubricant oil composition, in which a phenol-based antioxidant and/or an amine-based antioxidant are contained by 0.3 mass % or more of the total amount of the composition; (5) the above-described lubricating oil composition, in which the boron derivative of the polybutenyl succinimide compound is
• the lubricating oil composition according to the aspect of the invention exhibits excellent detergency for engine parts such as a piston in the internal combustion engine using so-called biofuel made of natural fat and oil and the like even when the biofuel is mixed into the engine oil.
• the lubricating oil is excellent in high-temperature detergency when the engine reaches a high temperature.
• the lubricating oil composition of the invention even when used in a diesel engine with a DPF, the lubricating oil composition can reduce residual ash content on the DPF, thereby preventing performance of the DPF from being deteriorated.
• Natural fat and oil used in the invention is not limited to plant-derived fat and oil but may include animal-derived fat and oil.
• a lubricating oil composition according to the invention is a lubricating oil composition used in an internal combustion engine, the internal combustion engine using a fuel that contains at least one fat and oil selected from a group consisting of natural fat and oil, hydrotreated natural fat and oil, transesterified natural fat and oil and hydrotreated transesterified natural fat and oil.
• the natural fat and oil may be a variety of animal-derived or plant-derived fat and oil that is generally available in nature
• the natural fat and oil is preferably plant oil that contains ester of fatty acid and glycerin as a major ingredient, examples of which are safflower oil, soybean oil, canola oil, palm oil, palm kernel oil, cotton oil, cocoanut oil, rice bran oil, benne oil, castor oil, linseed oil, olive oil, wood oil, camellia oil, earthnut oil, kapok oil, cacao oil, haze wax, sunflower seed oil, corn oil and the like.
• the hydrotreated natural fat and oil is formed by hydrogenating the above fat and oil under the presence of a suitable hydrogenating catalyst.
• the hydrogenating catalyst is exemplified by a nickel-based catalyst, a platinum family (Pt, Pd, Rh, Ru) catalyst, a cobalt-based catalyst, a chrome-oxide based catalyst, a copper-based catalyst, an osmium-based catalyst, an iridium-based catalyst, a molybdenum-based catalyst and the like.
• a combination of two or more of the catalysts may also be preferably used as the hydrogenating catalyst.
• the transesterified natural fat and oil is ester formed by transesterifying triglyceride contained in the natural fat and oil under the presence of a suitable ester-synthesis catalyst.
• a suitable ester-synthesis catalyst for instance, by transesterifying lower alcohol and the fat and oil under the presence of the ester-synthesis catalyst, fatty acid ester usable as biofuel is manufactured.
• the lower alcohol which is used as an esterifying agent, is exemplified by alcohol having 5 or less carbon atoms such as methanol, ethanol, propanol, butanol, pentanol and the like. In view of reactivity and cost, methanol is preferable.
• the lower alcohol is generally used in an amount equivalent to the fat and oil or more.
• the hydrotreated transesterified natural fat and oil is formed by hydrogenating the above transesterified fat and oil under the presence of a suitable hydrogenating catalyst.
• the natural fat and oil, the hydrotreated natural fat and oil, the transesterified natural fat and oil, and the hydrotreated transesterified natural fat and oil can be preferably used as mixed fuel by adding the above to fuel formed of hydrocarbon such as light oil.
• a base oil of lubricating oil employed for the lubricating oil composition according to the invention at least includes polyol ester and/or polybasic acid ester.
• polyol ester examples include an ester of alihphatic polyhydric alcohol and linear or branched fatty acid.
• examples of the aliphatic polyhydric alcohol that form this polyol ester include neopentyl glycol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, pentaerythritol, dipentaerythritol, and tripentaerythritol.
• Fatty acid having 8 to 12 carbon atoms may be employed, and examples of preferable fatty acid include pelargonic acid, capric acid, undecylic acid, lauric acid, and tridecyl acid.
• Partial ester of the above-noted aliphatic polyhydric alcohol and linear or branched fatty acid may also be employed. This partial ester can be obtained by reaction of aliphatic hydric alcohol and fatty acid accompanied by suitable adjustment of a reaction mol number.
• kinematic viscosity at 100 degrees C. is in the range of 3 to 8 mm 2 /s, preferably is in the range of 4 to 7 mm 2 /s, and further preferably in the range of 5 to 6 mm 2 /s.
• a kinematic viscosity at 100 degrees C. is 3 mm 2 /s or more, evaporation loss is small.
• the kinematic viscosity at 100 degrees C. is 8 mm 2 /s or less, power loss due to viscosity resistance is restricted, thereby improving fuel efficiency.
• a caroboxylic acid content preferably is linear or branched aliphatic dibasic acid having 6 to 10 carbon atoms. Specific examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and others that have the same property as these.
• An alcohol content preferably is aliphatic alcohol having 6 to 15 carbon atoms. Specific examples include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, and isomers thereof.
• kinematic viscosity at 100 degrees C. is in the range of 3 to 8 mm 2 /s, preferably is in the range of 4 to 7 mm 2 /s, and further preferably in the range of 5 to 6 mm 2 /s.
• a kinematic viscosity at 100 degrees C. is 3 mm 2 /s or more, evaporation loss is small.
• the kinematic viscosity at 100 degrees C. is 8 mm 2 /s or less, power loss due to viscosity resistance is restricted, thereby improving fuel efficiency.
• polyol ester and polybasic acid ester may respectively be used as a base oil alone or be used in a mixture, for example, in complex ester.
• Complex ester is ester synthesized from polybasic acid and polyhydric alcohol, usually including monobasic acid.
• complex ester favorably used may be formed from: aliphatic polyhydric alcohol; and linear or branched aliphatic monocarboxylic acid having 8 to 12 carbon atoms, linear or branched aliphatic dibasic acid, or aromatic dibasic acid, tribasic or tetrabasic acid.
• aliphatic polyhydric alcohol used to form complex ester examples include trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol.
• the aliphatic monocarboxylic acid may be aliphatic carboxylic acid having 8 to 12 carbon atoms, examples of which include heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, and lignoceric acid.
• Examples of aliphatic dibasic acid include succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, carboxylic octadecane acid, carboxymethyl octadecane acid, and docosanedioic acid.
• aromatic dibasic acid include phthalic acid, isophtahlic acid.
• Examples of aromatic tribasic acid include torimellitic acid.
• Examples of aromatic tetrabasic acid include pyromellitic acid.
• preferable viscosity range is the same as those of polyol ester and polybasic acid ester as described above.
• alcohol e.g., polyhydric alcohol
• carboxylic acid e.g., aliphatic polybasic ester or aromatic polybasic acid
• Contained amount of the above-described polyol ester and/or polybasic acid ester is in the range of 5 to 30 mass % relative to a total amount of the lubricating oil composition, preferably is in the range of 10 to 25 mass %, and further preferably is in the range of 10 to 20 mass %.
• the contained amount of polyol ester and/or polybasic acid ester is 5 mass % or less, sufficient detergency in an engine at a high temperature cannot be obtained.
• the contained amount of polyol ester and/or polybasic acid ester is more than 30 mass %, an influence on rubber is unfavorably increased.
• the basic oil may be suitably selected from a mineral oil and a synthetic oil used as a basic oil for a lubricating oil for an internal combustion engine to be mixed with the above-described polyol ester or polybasic acid ester.
• Examples of the mineral oil include: a mineral oil refined by processing lubricating oil fractions by at least one of solvent-deasphalting, solvent-extracting, hydrocracking, solvent-dewaxing, catalytic-dewasing and hydrorefining (the lubricating oil fractions are obtained by vacuum-distilling atmospheric residual oil obtained by atmospherically distilling crude oil); and a mineral oil manufactured by isomerizing wax and GTL (gas-to-liquid) WAX.
• examples of the synthetic oil include polybutene, polyolefin (e.g., ⁇ -olefin homopolymer or copolymer), various ethers (such as polyphenylether), polyglycol, alkylbenzene, and alkyl naphthalene.
• polyolefin is particularly preferable in view of viscosity characteristic and vaporizability.
• one of the above mineral oils may be singularly used or a combination of two or more thereof may be used as the base oil to be mixed with polyol ester and polybasic acid ester.
• one of the above synthetic oil may be singularly used or a combination of two or more thereof may be used.
• a combination of at least one of the above mineral oil and at least one of the above synthetic oil may be used.
• the base oil mixed with polyol ester and polybasic acid ester oil whose % CA measured by a ring analysis is 3 or less and whose sulfur content is 50 ppm by mass or less can be preferably used.
• the % CA measured by the ring analysis means a proportion (percentage) of aromatic content calculated by the n-d-M method (a ring analysis).
• the sulfur content is measured based on Japanese Industrial Standard (hereinafter called, JIS) K 2541.
• the sulfur content is more preferably 30 ppm by mass or less.
• the % CA is more preferably 1 or less, further more preferably 0.5 or less.
• viscosity index of polyol ester, polybasic acid ester, and the base oil mixed with these and used is preferably 70 or more, more preferably 100 or more, further more preferably 120 or more.
• the base oil whose viscosity index is 70 or more a viscosity change due to a temperature change is small.
• a lubricating oil composition of the invention preferably includes: a boron derivative of polybutenyl succcinimide compound whose polybutenyl group has a number average molecular weight of 500 to 3500 and whose mass ratio (B/N) between boron (B) and nitrogen (N) is 0.5 or more; and an alkaline earth metal detergent.
• Such a boron derivative of the polybutenyl succinimide compound can be obtained by, for example, reacting (a) a succinic acid substituted by a polybutenyl group having the number average molecular weight of 500 to 3500 or an anhydride of the succinic acid, (b) polyalkylene polyamine and (c) a boron compound.
• the succinic acid substituted by the polybutenyl group or an anhydride of the succinic acid is used as the material (a).
• the number average molecular weight (hereinafter may be abbreviated as molecular weight or Mn) of the polybutenyl group is typically 500 to 3500, preferably 1000 to 3000.
• Mn number average molecular weight
• the molecular weight of the polybutenyl group is less than 500, the eventually-obtained boron derivative of the succinimide compound may not be sufficiently dissolved in the base oil of the lubricating oil.
• the molecular weight is more than 3500, the succinimide compound may become so highly viscous as to impair the usability.
• the polybutenyl substituted succinic acid or an anhydride of the succinic acid as the material (a) may be obtained by reacting polybutene having the molecular weight equivalent to that of the polybutenyl group with maleic anhydride by a conventional method.
• polyalkylene polyamine is used for the material (b), 5 mol % or more of the total material is preferably formed from polyalkylene polyamine having a terminal ring structure.
• the entirety of the material (b) may be formed from polyalkylene polyamine having a terminal ring structure, or may be a mixture of polyalkylene polyamine having a terminal ring structure and polyalkylene polyamine having no terminal ring structure.
• polyalkylene polyamine having a terminal ring structure is contained by 5 mol % or more, engine-parts detergency is further improved, which is an object of the invention.
• the content of the polyalkylene polyamine is 10 mol % or more, further 20 mol % or more, the detergency is further improved, especially detergency at a high temperature is enhanced.
• a boron compound is used as the material (c).
• the boron compound are boracic acid, boric anhydride, borate ester, boric oxide and boron halogenide.
• boracic acid is particularly preferable.
• the boron derivative of polybutenyl succinimide according to the invention can be obtained by reacting the materials (a), (b) and (c). Without special limitations, any known methods of reacting can be used. For instance, by reacting the materials by the following manner, the target substance can be obtained. The materials (a) and (b) are initially reacted with each other, then its reaction product is reacted with the material (c). A mixing ratio of the materials (a) to (b) in the reaction of the material (a) and (b) is preferably 0.1-to-10 to 1 (mole ratio), more preferably 0.5-to-2 to 1 (mole ratio).
• a reaction temperature of the materials (a) and (b) is preferably in a range of approximately 80 to 250 degrees C, more preferably in a range of approximately 100 to 200 degrees C.
• solvents such as an organic solvent exemplified by hydrocarbon oil may be used as necessary.
• reaction product of the materials (a) and (b) is reacted with the material (c).
• a mixing ratio of polyalkylene polyamine to the boron compound as the reaction material (c) is typically 1 to 0.05-to-10, preferably 1 to 0.5-to-5 (mole ratio).
• a reaction temperature therefor is typically approximately 50 to 250 degrees C, preferably 100 to 200 degrees C.
• solvents such as an organic solvent exemplified by hydrocarbon oil may be used as necessary.
• a boron derivative of a succinimide compound substituted by a polybutenyl group having a number average molecular weight of 200 to 3500 is obtained.
• one of the boron derivative may be singularly used or a combination of two or more thereof may be used.
• the content of boron derivative of polybutenyl succinimide compound in the lubricating composition of the invention preferably is 0.01 mass % or more in terms of boron (atoms) relative to the total amount of the composition.
• boron derivative Since a predetermined amount or more of boron is contained in the boron derivative, even when biofuel is mixed into the lubricating oil composition, favorable piston detergency can be obtained in an internal combustion engine at a high temperature.
• the content of boron derivative is less than 0.01 mass %, sufficient high-temperature detergency cannot be obtained.
• the content of boron exceeds 0.2 mass %, no further improvement is made on the high-temperature detergency, which is of little practical use.
• a mass ratio (B/N) of boron (B) contained in the boron derivative and nitrogen (N) is preferably 0.5 or more, more preferably 0.6 or more, further more preferably 0.8 or more.
• B/N is 0.5 or more, high-temperature detergency for engine parts is greatly enhanced.
• a boronated succinimide-based compound can be obtained by initially reacting the materials (a) and (b) and subsequently reacting the reaction product thereof with the material (c), the reaction order may be changed such that the materials (a) and (c) are initially reacted and the reaction product thereof is subsequently reacted with the material (b). With this reaction order, the target boronated succinimide compound may be likewise obtained.
• An alkaline earth metal detergent as well as the polybutenyl succinide compound preferably is mixed to the lubricating oil composition of the invention.
• alkaline earth metal detergent examples include one selected from a group consisting of alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate and a mixture of two or more selected from the group.
• alkaline earth metal sulfonate is alkaline earth metal salt of alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 to 1500 (preferably 400 to 700).
• the alkaline earth metal salt is exemplified by magnesium salt and/or calcium salt and the like, among which calcium salt is preferably used.
• alkaline earth metal phenate is alkaline earth metal salt of alkylphenol, alkylphenol sulfide and a Mannich reaction product of alkylphenol.
• the alkaline earth metal salt is exemplified by magnesium salt and/or calcium salt and the like, among which calcium salt is preferably used.
• alkaline earth metal salicylate is alkaline earth metal salt of alkyl salicylic acid.
• the alkaline earth metal salt is exemplified by magnesium salt and/or calcium salt and the like, among which calcium salt is preferably used.
• An alkyl group forming the alkaline earth metal-based detergent preferably has 4 to 30 carbon atoms.
• the alkyl group is more preferably a linear or branched alkyl group having 6 to 18 carbon atoms, in which 6 to 18 carbon atoms may be in a linear chain or in a branched chain.
• the alkyl group may be a primary alkyl group, a secondary alkyl group or a tertiary alkyl group.
• alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate may be neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate obtained by: directly reacting the above-described alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, a Mannich reaction product of alkylphenol, alkyl salicylic acid or the like with alkaline earth metal base exemplified by an oxide or a hydroxide of alkaline earth metal such as magnesium and/or calcium; or converting the above-described substance into alkali metal salt such as sodium salt or potassium salt and subsequently substituting the alkali metal salt with alkaline earth metal salt.
• alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate may be: basic alkaline earth metal sulfonate, basic alkaline earth metal phenate and basic alkaline earth metal salicylate obtained by heating neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate with excess alkaline earth metal salt or alkaline earth metal base under the presence of water; or overbased alkaline earth metal sulfonate, overbased alkaline earth metal phenate and overbased alkaline earth metal salicylate obtained by reacting neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate with carbonate or borate of alkaline earth metal under the presence of carbon dioxide gas.
• the content of the alkaline earth metal-based detergent is preferably 0.35 mass % or less in terms of alkaline earth metal, more preferably 0.01 to 0.35 mass %, further more preferably 0.1 to 0.35 mass %.
• the content of the alkaline earth metal-based detergent is 0.01 mass % or more, the lubricating oil composition exhibits more excellent oxidation stability, base-number retention and high-temperature detergency.
• the content of the alkaline earth metal-based detergent exceeds 0.35 mass %, performance of catalyst for purifying exhaust gas may be deteriorated.
• an amount of ash content adhering to the DPF may be increased, thereby shortening the life of the DPF.
• the lubricating oil composition according to the invention preferably contains a phenol-based antioxidant and/or an amine-based antioxidant as the antioxidant.
• phenol-based antioxidant examples include: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 4,4′-methylenebis(2,6-di-t-butylphenol); 4,4′-bis(2,6-di-t-butylphenol); 4,4′-bis(2-methyl-6-t-butylphenol); 2,2′-methylenebis(4-ethyl-6-t-butylphenol); 2,2′-methylenebis(4-methyl-6-t-butylphenol); 4,4′-butylidenebis(3-methyl-6-t-butylphenol); 4,4′-isopropylidenebis(2,6-di-t-butylphenol); 2,2′-methylenebis(4-methyl-6-nonylphenol); 2,2′-isobutylidenebis(4,6-dimethylphenol); 2,2′-methylenebis(4-methyl-6-cyclohexylphenol);
• amine-based antioxidant examples include: an antioxidant based on monoalkyldiphenylamine such as monooctyldiphenylamine and monononyldiphenylamine; an antioxidant based on dialkyl diphenylamine such as 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine and 4,4′-dinonyldiphenylamine; an antioxidant based on polyalkyldiphenylamine such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine and tetranonyldiphenylamine; and an antioxidant based on naphthylamine, specifically alkyl-substituted phenyl-
• a molybdenum-amine complex-based antioxidant may be used as another antioxidant.
• a molybdenum-amine complex-based antioxidant a hexahydric molybdenum compound, an example of which is a reaction product obtained by reacting molybdenum trioxide and/or molybdenum acid with an amine compound, may be used.
• the reaction product may be, for example, a compound obtained by the manufacturing method disclosed in JP-A-2003-252887.
• the amine compound to be reacted with the hexahydric molybdenum compound subjects to no particular limitation, and examples thereof are monoamine, diamine, polyamine and alkanolamine.
• the amine compound are: alkyl amine having an alkyl group of 1 to 30 carbon atoms (the alkyl group may contain a linear chain or a branched chain), exemplified by methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, methylpropylamine and the like, alkenyl amine having an alkenyl group of 2 to 30 carbon atoms (the alkenyl group may contain a linear chain or a branched chain), exemplified by ethenylamine, propenylamine, butenylamine, octenylamine and oleylamine, alkanol amine having an alkanol group of 1 to 30 carbon atoms (the alkanol group may contain a linear chain or a branched chain), exemplified by methanolamine, ethanolamine, methanolethanolamine and methanolpropanolamine; alkylenediamine having an
• a mixing content of the antioxidant is preferably 0.3 mass % or more of the total amount of the composition, more preferably 0.5 mass % or more.
• the content of the antioxidant is preferably in a range from 0.3 to 2 mass % of the total amount of the composition.
• the lubricating oil composition according to the invention may be added as necessary with other additives such as a viscosity index improver, a pour point depressant, antiwear agent, an ashless-type friction modifier, a rust inhibitor, a metal deactivator, a surfactant and antifoaming agent as long as effects of the invention are not hampered.
• additives such as a viscosity index improver, a pour point depressant, antiwear agent, an ashless-type friction modifier, a rust inhibitor, a metal deactivator, a surfactant and antifoaming agent as long as effects of the invention are not hampered.
• the viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, an olefin-based copolymer (such as an ethylene-propylene copolymer), a dispersed olefin-based copolymer, a styrene-based copolymer (such as a styrene-diene copolymer and a styrene-isoprene copolymer) and the like.
• a content of the viscosity index improver is 0.5 to 15 mass % of the total amount of the composition, preferably 1 to 10 mass %.
• pour point depressant is polymethacrylate having a weight-average molecular weight of 5000 to 50000.
• the antiwear agent examples include: sulfur-containing compounds such as zinc dithiophosphate, zinc dithiocarbamate, zinc phosphate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates (such as Mo-DTC) and the like; phosphorus-containing compounds such as phosphite esters, phosphate esters, phosphonate esters and amine salts or metal salts thereof; and a sulfur and phosphorus-containing antiwear agent such as thiophosphite esters, thiophosphate esters (such as Mo-DTP), thiophosphonate esters and amine salts or metal salts thereof
• any compounds generally used as the ashless-type friction modifier for lubricating oil may be used, examples of which are fatty acid, aliphatic alcohol, aliphatic ether, aliphatic ester, aliphatic amine and aliphatic
• rust inhibitor examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic ester, multivalent alcohol ester and the like.
• a content of the rust inhibitor is generally 0.01 to 1 mass % of the total amount of the composition, preferably 0.05 to 0.5 mass %.
• the metal deactivator (copper corrosion inhibitor) are benzotriazole-based compounds, tolyltriazole-based compounds, thiadiazole-based compounds, imidazole-based compounds, and pyrimidine-based compounds.
• the benzotriazole-based compounds are preferable.
• a content of the metal deactivator is preferably 0.01 to 0.1 mass % of the total amount of the composition, more preferably 0.03 to 0.05 mass %.
• surfactant examples include nonionic surfactants based on polyalkylene glycol such as polyoxyethylenealkylether, polyoxyethylenealkylphenylether and polyoxyethylenealkylnaphthylether.
• a content of the antifoaming agent is preferably approximately 0.005 to 0.1 mass % of the total amount of the compound.
• Sulfur content of the lubricating oil composition according to the invention is preferably 0.5 mass % or less of the total amount of the composition, more preferably 0.3 mass % or less, further more preferably 0.2 mass % or less.
• sulfur content is 0.5 mass % or less, deterioration of the catalyst performance for purifying exhaust gas can be effectively prevented.
• Phosphorus content of the lubricating oil composition according to the invention is preferably 0.12 mass % or less of the total amount of the composition, more preferably 0.1 mass % or less.
• the phosphorus content is 0.12 mass % or less, deterioration of the catalyst performance for purifying exhaust gas can be effectively prevented.
• Sulfated ash content of the lubricating oil composition according to the invention is preferably 1.1 mass % or less, more preferably 1 mass % or less.
• sulfated ash content is 1.1 mass % or less, deterioration of the catalyst performance for purifying exhaust gas can be effectively prevented.
• the ash content accumulated on the filter of the DPF can be reduced, thereby preventing the filter blockage due to the ash content and contributing to a long life of the DPF.
• the sulfated ash content means ash content obtained by adding sulfuric acid to carbonized residue caused by combustion of samples for heating so that the residue has a constant mass.
• the sulfated ash is generally used to know a rough amount of metal-based additives contained in the lubricating oil composition. Specifically, the sulfated ash is measured by a method prescribed in “5. Experiment Method of Sulfated Ash” of JIS K 2272.
• NOACK evaporation measured according to JPI (abbreviation for Japan Petroleum Insititute, the same applies hereinafter)-5S-41-93 is preferably 15 mass % or less, more preferably 13 mass % or less, and further preferably 10 mass % or less.
• Lubricating oil compositions containing components shown in Table 1 respectively were prepared, which were then subjected to such a hot tube test as follows.
• the components used for preparing the lubricating oil compositions are as follows.
• Base Oil A hydrorefining base oil; kinematic viscosity at 40 degrees C. of 21 mm 2 /s; kinematic viscosity at 100 degrees C. of 4.5 mm 2 /s; viscosity index of 127; % CA of 0.0; sulfur content of less than 20 ppm by mass; and NOACK evaporation of 13.3 mass %.
• Base Oil B PAO; kinematic viscosity at 40 degrees C. of 17.5 mm 2 /s; kinematic viscosity at 100 degrees C. of 3.9 mm 2 /s; viscosity index of 120; and NOACK evaporation of 15 mass %.
• Base Oil C ester oil (polyol fatty acid ester; polyol content being trimethylolpropane, and fatty acid content being refined cocoanut oil (of C8 to C12)); kinematic viscosity at 40 degrees C. of 19.8 mm 2 /s; kinematic viscosity at 100 degrees C. of 4.3 mm 2 /s; viscosity index of 139; NOACK evaporation of 3 mass %; and saponification number of 0.1 mg KOH/g.
• Base Oil D tridecyl adipate; kinematic viscosity at 40 degrees C. of 27 mm 2 /s; kinematic viscosity at 100 degrees C.
• Viscosity Index Improver polymethacrylate; mass average molecular weight of 420000; and resin content of 39 mass %.
• Pour Point Depressant polyalkylmethacrylate; and mass average molecular weight of 6000.
• Metal-Based Detergent overbased calcium salicylate; base number of 225 mg KOH/g (perchloric acid method); calcium content of 7.8 mass %; and sulfur content of 0.3 mass %.
• Polybutenyl Succinic Monoimide A number average molecular weight of the polybutenyl group being 1000; nitrogen content of 1.76 mass %; boron content of 2.0 mass %; and B/N of 1.1.
• Polybutenyl Succinic Bisimide B number average molecular weight of the polybutenyl group being 2000; nitrogen content of 0.99 mass %; and B/N of 0.
• Phenol-Based Antioxidant octadecyl-3-(3,5-tert-butyl-4-hydroxyphenyl)propionate.
• Amine-Based Antioxidant dialkyl diphenylamine; nitrogen content of 4.62 mass %.
• Zinc Dialkyl Dithio Phosphate Zn content of 9.0 mass %; phosphorus content of 8.2 mass %; sulfur content of 17.1 mass %; and the alkyl group being a mixture of a secondary butyl group and a secondary hexyl group.
• Copper Corrosion Inhibitor 1-[N,N-bis(2-ethylhexyl) aminomethyl]methyl benzotriazole.
• Biodiesel Fuel canola oil methyl ester.
• Other Additives a rust inhibitor, a surfactant and an antifoaming agent.
• lubricating oil composition to be tested mixed oil in which biofuel (fuel obtained by transesterifying canola oil with methyl alcohol) was mixed by 5 mass % of each of the lubricating oil compositions (new oil) was used, assuming a mixing ratio of the fuel and the lubricating oil in an internal combustion engine.
• the measurement was conducted with the test temperature being set at 280 degrees C. and 320 degrees C, and other conditions being based on JPI-5S-55-99.
• the hot tube test may be affected by the amount of the viscosity index improver, the content of the viscosity index improver was made constant among Examples and Comparatives. The smaller an amount of fouling on the glass tube after the test was, the more favorable the detergency is.
• the lubricating oil composition according to the present invention is favorably applied to an internal combustion engine in which biofuel or biofuel-mixed fuel is employed.

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