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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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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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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—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
  • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
  • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic 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
  • C10M2207/40—Fatty vegetable or animal oils
  • C10M2207/401—Fatty vegetable or animal oils used as base material
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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
  • C10M2215/086—Imides
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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
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  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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  • 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
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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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  • 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
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  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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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
  • C10N2030/45—Ash-less or low ash content
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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
  • C10N2040/252—Diesel engines
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  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/02—Reduction, e.g. hydrogenation

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 In line with an idea of carbon neutral advocating that carbon dioxide generated due to combustion of plant biomass is not counted as a contributor to an increase of the global warming gas, ratio at which the biofuel is mixed in hydrocarbon fuel is expected to be increased in the future (for instance, see Non-Patent Document 1).
• 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.
• post-injection of fuel is generally conducted so as to combust the soot accumulated on the filter.
• Engine oil is diluted by the fuel due to the post-injection, so that performance of the engine oil is expected to be lowered.
• biofuel since biofuel can be easily accumulated in the engine oil due to its property and generates polar compounds when degraded and decomposed, the biofuel may adversely affect corrosion of engine parts such as a piston. Also, the filter is likely to be clogged by a metal oxide, hydrosulfate, carboxylate or the like generated in the combustion.
• metal content or sulfur content in lubricating oil is as low as possible. Thus, it is preferable to decrease phosphorus content or sulfur content in the lubricating oil in order to prevent degrading of exhaust gas purifying catalyst.
• lubricating oil sufficiently adapted for use with biofuel has not been provided yet.
• An object of the invention is to provide a lubricating oil composition capable of reducing corrosion of engine parts even when biofuel or biofuel-mixed fuel is used in an internal combustion engine such as a diesel engine.
• a lubricating oil composition as follows is provided according to an aspect of the invention.
• the lubricating oil composition according to the aspect of the present invention is corrosive-resistant to engine parts such as a piston in the internal combustion engine using biofuel made of natural fat and oil and the like even when the biofuel is mixed into the engine oil.
• the lubricating oil composition according to the aspect 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 of 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 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, and corn oil.
• 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. Two or more of the catalysts may also be preferably combined to be 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. 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.
• Base oil used in the lubricating oil composition according to the invention is not particularly limited but may be suitably selected from any mineral oil and synthetic oil that have been traditionally used as base oil of the lubricating oil for the internal combustion engine.
• the mineral oil include: mineral oil refined by processing lubricating oil fractions, which are obtained by vacuum-distilling atmospheric residual oil obtained by atmospherically distilling crude oil, by at least one of solvent-deasphalting, solvent-extracting, hydrocracking, solvent-dewaxing, catalytic-dewasing and hydrorefining; and mineral oil manufactured by isomerizing wax and GTL (gas-to-liquid) WAX.
• examples of the synthetic oil include polybutene, polyolefin ( ⁇ -olefin homopolymer or copolymer such as ethylene- ⁇ -olefin copolymer), various esters (such as polyol ester, diacid ester and phosphoric ester), various ethers (such as polyphenylether), polyglycol, alkylbenzene, and alkyl naphthalene.
• polyolefin and polyol ester are particularly preferable.
• One of the above mineral oil may be singularly used or two or more thereof may be combined to be used as the base oil.
• one of the above synthetic oil may be singularly used or two or more thereof may be combined to be used. Further, at least one of the above mineral oil and at least one of the above synthetic oil may be combined for use.
• kinetic viscosity of the base oil subjects to no specific limitation and varies depending on usage of the lubricating oil composition
• kinetic viscosity thereof at 100 degrees C is generally preferably 2 to 30 mm 2 /s, more preferably 3 to 15 mm 2 /s, much more preferably 4 to 10 mm 2 /s.
• the kinetic viscosity at 100 degrees C is 2 mm 2 /s or more, evaporation loss is small.
• the kinetic viscosity at 100 degrees C is 30 mm 2 /s or less, power loss due to viscosity resistance is restricted, thereby improving fuel efficiency.
• the base oil 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 JIS (abbreviation for Japanese Industrial Standard) K 2541.
• the base oil whose %CA is 3 or less and whose sulfur content is 50 ppm by mass or less exhibits a favorable oxidation stability. Such base oil can restrict an increase of acid number and a generation of sludge, thereby providing a lubricating oil composition that is less corrosive to metal.
• 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 the base oil is preferably 70 or more, more preferably 100 or more, much more preferably 120 or more. In the base oil whose viscosity index is 70 or more, a viscosity change due to a temperature change is small.
• a sulfur compound containing at least one -C-S-C-bond is added in the above-described base oil.
• Such a sulfur compound is preferably dissolved or uniformly dispersed in the base oil of the lubricating oil.
• sulfur compound may include sulfurized fat and oil, a sulfurized fatty acid, an ester sulfide, an olefin sulfide, a dihydrocarbyl monosulfide, a thiadiazole compound, a thiophosphate ester (thiophosphite, thiophosphate), an alkylthiocarbamoyl compound, a thiocarbamate compound, a thioterpene compound and a dialkyl thiodipropionate compound.
• a sulfur compound used as a sulfuric antioxidant is preferable.
• the sulfurized fat and oil may be obtained by reacting fat and oil (e.g., lard oil, whale oil, vegetable oil and fish oil) with sulfur or a sulfur-containing compound.
• a content of the sulfur is not particularly limited, but 5 to 30 mass% is generally preferable.
• Concrete examples of the sulfurized fat and oil may include a surfurized lard, a sulfurized rape seed oil, a sulfurized castor oil, a sulfurized soybean oil and a sulfurized rice bran oil.
• the sulfurized fatty acid may be exemplified by a sulfurized oleic acid, while the ester sulfide may be exemplified by a sulfurized methyl oleate, a sulfurized rice bran fatty acid octyl and a ditridecyl thiodipropionate.
• Examples of the olefin sulfide preferably used according to the invention include a compound represented by the following formula (1).
• R 1 -S-R 2 (1)
• R 1 represents an alkenyl group having 2 to 15 carbon atoms
• R 2 represents an alkyl group or an alkenyl group having 2 to 15 carbon atoms.
• the compound can be obtained by reacting an olefin having 2 to 15 carbon atoms or a dimer to a tetramer thereof with a sulfurizing agent such as sulfur, sulfur chloride and the like.
• the olefin may preferably be propylene, isobutene, and diisobutene.
• Examples of the dihydrocarbyl monosulfide include a compound represented by the following formula (2).
• R 3 and R 4 each represent an alkyl group or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl aryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, which may be mutually the same or different.
• R 3 and R 4 are alkyl groups, the compound is also referred to as an alkyl sulfide.
• R 3 and R 4 in the formula (2) may include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, cyclohexyl group, cyclooctyl group, phenyl group, naphthyl group, tolyl group, xylyl group, benzyl group and phenethyl group.
• Examples of the dihydrocarbyl monosulfide may include dibenzyl monosulfide, various dinonyl monosulfides, various didodecyl monosulfides, various dibutyl monosulfides, various dioctyl monosulfides, diphenyl monosulfide and dicyclohexyl monosulfide.
• Examples of the thiadiazole compound may preferably include 1,3,4-thiadiazole, 1,2,4-thiadiazole compound, and 1,4,5-thiadiazole represented by the following formulae (3) to (5).
• R 5 to R 6 each represent a hydrocarbon group having 1 to 20 carbon atoms.
• the thiadiazole compound may include 2,5-bis(n-hexyldithio)-1,3,4-thiadiazole, 2,5-bis(n-octyldithio)-1,3,4-thiadiazole, 2,5-bis(n-nonyldithio)-1,3,4-thiadiazole, 2,5-bis-(1,1,3,3-tetramethylbutyldithio)-1,3,4-thiadiazole, 3,5-bis(n-hexyldithio)-1,2,4-thiadiazole, 3,5-bis(n-octyldithio)-1,2,4-thiadiazole, 3,5-bis(n-nonyldithio)-1,2,4-thiadiazole, 3,5-bis-(1,1,3,3-tetramethylbutyldithio)-1,2,4-
• Examples of the thiophosphate ester may include an alkyl trithiophosphite, an aryl or alkyl aryl thiophosphate, and a zinc dilauryldithiophosphate. Particularly, a lauryl trithiophosphite and a triphenyl thiophosphate are preferable.
• the alkylthiocarbamoyl compound may be exemplified by a compound represented by the following formulae (6) and (7).
• R 7 to R 10 each represent an alkyl group having 1 to 20 carbon atoms.
• R 11 represents an alkylene group having 1 to 20 carbon atoms.
• the alkylthiocarbamoyl compound may preferably include a bis(dimethylthiocarbamoyl)monosulfide, a bis(dibutylthiocarbamoyl)monosulfide, a bis(dimethylthiocarbamoyl)monosulfide, a bis(dibutylthiocarbamoyl)monosulfide, a bis(diamylthiocarbamoyl)monosulfide, a bis(dioctylthiocarbamoyl)monosulfide, and a methylene bis(dibutyldithiocarbamate).
• the thiocarbamate compound may be exemplified by, for instance, a zinc dialkyldithiocarbamate.
• the thioterpene compound may be exemplified by, for instance, a reaction product of a phosphorus pentasulfide or pinene.
• the dialkyl thiodipropionate compound may be exemplified by, for instance, dilauryl thiodipropionate, or distearyl thiodipropionate.
• the content of the above-described sulfur compound is 0.3 mass% or less in terms of sulfur contained in the -C-S-C-bond in the compound of the total amount of the composition.
• the content of the sulfur is preferably 0.05 to 0.2 mass%.
• the sulfur compound preferably does not contain a -C-S X -C-bond (x is an integer of 2 or more).
• a sulfur compound having a polysulfide structure is not preferable in light of corrosivity of engine parts. Especially, under the presence of the biofuel, an elution amount of copper and lead is increased.
• the lubricating oil composition according to the invention preferably contains an alkaline earth metal-based detergent.
• the alkaline earth metal-based detergent include alkaline earth metal sulfonate, alkaline earth metal phenate, alkaline earth metal salicylate and a mixture of two or more thereof.
• the alkaline earth metal sulfonate include 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. Particularly, calcium salt is preferably used.
• alkaline earth metal phenate examples include 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. Particularly, calcium salt is preferably used.
• alkaline earth metal salicylate examples include alkaline earth metal salt of alkyl salicylic acid, which is exemplified by magnesium salt and/or calcium salt. Particularly, 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.
• the 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 are: 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(2,5-di-t-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobuty
• 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 based on the total amount of the composition, more preferably 0.5 mass% or more. When the content exceeds 2 mass%, the antioxidant may not be dissolved in the base oil of the lubricating oil. Accordingly, the content of the antioxidant is preferably in a range from 0.3 to 2 mass% based on 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, an antiwear agent, an ashless-type friction modifier, a rust inhibitor, a metal deactivator, a surfactant and an antifoaming agent as long as advantageous effects of the invention are not hampered.
• additives such as a viscosity index improver, a pour point depressant, an antiwear agent, an ashless-type friction modifier, a rust inhibitor, a metal deactivator, a surfactant and an antifoaming agent as long as advantageous 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).
• a content of the viscosity index improver is 0.5 to 15 mass% based on the total amount of the composition, preferably 1 to 10 mass%.
• Examples of the pour point depressant include polymethacrylate having a mass average molecular weight of 5000 to 50000.
• Examples of the antiwear agent are: 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.
• the antiwear agent as described above may accelerate corrosion of the engine parts when being used with the sulfur compound according to the invention.
• Examples of the ashless-type friction modifier include a mono-type or bis-type polybutenyl succinimide and/or a boride thereof, a benzylamine, and a polyalkenylamine.
• the polybutenyl succinimide having a polybutenyl group having a mass average molecular weight of 700 to 3500 is preferable.
• Other examples of the ashless-type friction modifier are fatty acid, aliphatic alcohol, aliphatic ether, aliphatic ester, aliphatic amine and aliphatic amide, which have at least one alkyl or alkenyl group of 6 to 30 carbon atoms in the molecule.
• An ashless dispersant is preferably added in a range from 0.5 to 10 parts by mass relative to 100 parts by mass of the base oil.
• rust inhibitor examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic ester, multivalent alcohol ester.
• a content of the rust inhibitor is generally 0.01 to 1 mass% based on 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. Among the above, the benzotriazole-based compounds are preferable.
• the metal deactivator By adding the metal deactivator, the engine parts can be prevented from being metallically corroded and degraded due to oxidation.
• a metal deactivator is preferably used with the sulfur compound as specified above.
• a content of the metal deactivator is preferably 0.01 to 0.1 mass% based on 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 based on 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
• Phosphorus content of the lubricating oil composition according to the invention is preferably 0.12 mass% or less based on the total amount of the composition, more preferably 0.1 mass% or less. When the phosphorus content is 0.12 mass% or less, deterioration of the catalyst performance for purifying exhaust gas can be effectively prevented.
• Sulfate ash content of the lubricating oil composition according to the invention is preferably 1.1 mass% or less, more preferably 1 mass% or less.
• sulfate ash content is 1.1 mass% or less, deterioration of the catalyst performance for purifying exhaust gas can be effectively prevented.
• ash content accumulated on the filter of the DPF can be reduced, thereby preventing the filter blockage due to the ash and contributing to a long life of the DPF.
• the sulfate 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 sulfate ash is generally used to know a rough amount of metal-based additives contained in the lubricating oil composition. Specifically, the sulfate ash is measured by a method prescribed in "5. Experiment Method of Sulfate Ash" of JIS K 2272. Incidentally, when vaporizability of lubricating oil in an internal combustion engine is increased, more lubricating oil is consumed, which leads to a shortened lifetime of the lubricating oil. In addition, because more lubricating oil is dispersed within the exhaust gas catalyst, catalyst performance is lowered and catalyst lifetime is shortened.
• 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 corrosivity test as follows.
• the components used for preparing the lubricating oil compositions were as follows.
• lubricating oil composition to be tested mixed oil in which biofuel (fuel obtained by transesterifying canola oil with methyl alcohol) was mixed by 10 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.
• biofuel fuel obtained by transesterifying canola oil with methyl alcohol
• new oil 10 mass% of each of the lubricating oil compositions
• 100 g of the mixed oil was put as sample oil into a glass container (having a diameter of 40 mm and a height of 300 mm) and then air was blown into the glass container for 168 hours at 88 ml/min while the temperature of the oil is maintained at 125 degrees C.
• Examples 1 and 2 in which the lubricating oil composition according to the invention was used produced a slight amount of copper (Cu) and lead (Pb) eluted in the oil even when the lubricating oil composition to which biofuel was added was used.
• the elution amount of lead was small as compared with that in the lubricating oil composition to which no biofuel was added as in Reference Examples 1 and 2.
• the specified sulfur compound of the invention was not mixed as in Comparative 1, the elution amounts of copper and lead were increased.
• This 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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