Classifications

• • 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
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/54—Fuel economy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines

Definitions

• This invention relates to a lubricant oil composition, more specifically to a lubricant oil composition preferably used in an application such as a lubricant oil composition for an internal combustion engine.
• MoDTC molybdenum dithiocarbamate
• the object of the invention is to provide a lubricant oil composition capable of maximizing the friction reducing effect by optimizing a base oil and an additive other than a friction modifier used in a lubricant oil composition, particularly a lubricant oil composition for an internal combustion engine.
• the inventors have, as a result of devoted studies for achieving the above object, found that a lubricant oil composition capable of maximizing the friction reducing effect can be obtained by optimizing the sulfur content and the aromatic content of a base oil, and a certain metal-based detergent, and completed the invention.
• the invention is a lubricant oil composition containing:
• the carbon number of an alkyl chain of a soap group of the metal salicylate-based detergent (B) is not less than 10 as an average.
• the metal salicylate-based detergent (B) is an overbased calcium carbonate salicylate.
• the lubricant oil composition of the invention is preferable to be a lubricant oil composition for an internal combustion engine.
• the invention is a method for improving the fuel saving property of an internal combustion engine by using the above lubricant oil composition.
• a lubricant oil composition particularly a lubricant oil composition for an internal combustion engine, excellent in fuel saving property and capable of sufficiently reducing friction under boundary lubrication conditions and under mixed lubrication conditions even without a friction modifier.
• the lubricant oil composition of the invention contains a base oil (A) wherein the sulfur content is not less than 0.03 mass%, and the mass ratio [%C A (mass%)/sulfur content (mass%)] between the aromatic content (%C A ) and the sulfur content is not more than 30, and a metal salicylate-based detergent (B) in not more than 3 mass% as an alkali metal or alkali earth metal amount based on the total amount of the composition.
• A base oil
• B metal salicylate-based detergent
• the sulfur content is not less than 0.03 mass%, preferably not less than 0.1 mass%, further preferably not less than 0.2 mass%, further more preferably not less than 0.3 mass%, particularly preferably not less than 0.4 mass%, most preferably not less than 0.5 mass%. Also, in the based oil (A), the sulfur content is preferably not more than 1.2 mass%, further preferably not more than 1 mass%, further more preferably not more than 0.8 mass%, particularly preferably not more than 0.7 mass%.
• the sulfur content of the base oil (A) of not less than 0.03 mass% friction is reduced, and when it is used as a lubricant oil for an internal combustion engine, a lubricant oil composition excellent in fuel saving property can be obtained.
• the sulfur content of the base oil (A) of more than 1.2 mass% oxidation stability of the lubricant oil composition deteriorates, sludge and the like easily occur, which are not preferable.
• sulfur content herein refers to a value measured according to JIS K 2541-4 "Energy Dispersive X-ray Fluorescence Method " (normally, within a range of 0.01 to 5 mass%) or JIS K 2541-5 "General Bomb Method, Supplementary Notes (Rules), Inductively Coupled Plasma Atomic Emission Spectrometry " (normally, not less than 0.05 mass%).
• the mass ratio [%C A (mass%)/sulfur content (mass%)] between the aromatic content (%C A ) and the sulfur content is not more than 30, preferably not more than 15, more preferably not more than 12, and also, preferably not less than 5, more preferably not less than 7.
• the friction reducing effect increases, while with that of less than 5, the influence of sulfur becomes too much, and the friction coefficient is concerned to be large conversely.
• the %C A of the above base oil (A) is not particularly limited as long as it meets the ranges of the mass ratio [%C A (mass%)/sulfur content (mass%)] between the aromatic content (%C A ) and the sulfur content as described above, it is preferably not more than 20, more preferably not more than 15, particularly preferably not more than 10, in terms of oxidation stability. It should be noted that the %C A is obtained by a method according to ASTM D 3238 (n-d-M ring analysis).
• the base oil (A) of the lubricant oil composition of the invention is not limited as long as the sulfur content is not less than 0.03 mass% and the mass ratio [%C A (mass%)/sulfur content (mass%)] between the aromatic content (%C A ) and the sulfur content is not more than 30. Therefore, the base oil (A) may contain at least one kind of sulfur containing mineral base oils shown below, alone or in combination with one kind or two or more kinds of other mineral base oils or synthetic base oils.
• the above mineral base oil specifically includes one formed by vacuum distilling an atmospheric residue obtained by atmospheric distilling a crude oil to obtain a lubricant oil fraction, and refining it in one or more treatments such as solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing and hydrogenation refining.
• a base oil hardly containing sulfur a wax isomerized mineral oil, a base oil produced by a method of isomerizing GTL WAX (gas-to-liquid wax), a synthetic base oil, and the like can be exemplified.
• polybutene or hydride thereof poly- ⁇ -olefin such as 1-octene oligomer and 1-decene oligomer or hydride thereof; diester such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; polyol ester such as neopentyl glycol ester, trimethylol propane caprylate, trimethylol propane pelargonate, pentaerythritol-2-ethylhexanoate and pentaerythritol pelargonate; aromatic synthetic oil such as alkylnaphthalene, alkylbenzene, and aromatic ester or mixture thereof, and the like can be exemplified.
• diester such as ditridecyl glutarate, di-2-ethylhexyl
• the kinematic viscosity of the above base oil (A) is not particularly limited, its kinematic viscosity at 100°C is preferably not more than 20 mm 2 /s, more preferably not more than 15 mm 2 /s, particularly preferably not more than 10 mm 2 /s.
• the kinematic viscosity at 100°C of the base oil (A) is preferably not less than 1 mm 2 /s, more preferably not less than 2 mm 2 /s.
• the viscosity index of the above base oil (A) is not particularly limited and is normally not more than 200, its viscosity index is preferably not less than 80, further preferably not less than 100, particularly preferably not less than 120, so that excellent viscosity property can be obtained from a low temperature to a high temperature.
• the viscosity index of the base oil (A) is less than 80, low temperature viscosity property tends to deteriorate.
• the viscosity index of the base oil (A) is preferable to be not more than 160.
• the lubricant oil composition of the invention contains a metal salicylate-based detergent (B).
• a metal salicylate-based detergent (B) a metal salicylate represented by the following general formula (1), and/or its (over)basic salt are preferable.
• R 1 is an alkyl group or alkenyl group
• M represents an alkali metal or alkali earth metal, preferably calcium or magnesium, particularly preferably calcium
• n is 1 or 2.
• alkali metal or alkali earth metal salicylate preferably having one alkyl group or alkenyl group within a molecule, and/or its (over)basic salt are preferable.
• the method for producing the above alkali metal or alkali earth metal salicylate is not particularly limited, and a publicly known method for producing monoalkyl salicylate and the like can be used.
• the above alkali earth metal salicylate can be obtained by subjecting a monoalkylsalicylic acid obtained by using a phenol as a starting raw material, alkylating it using olefin and carboxylating it with a carbon dioxide gas and the like, a monoalkylsalicylic acid obtained by using a salicylic acid as a starting raw material and alkylating it using an equivalent of the above olefin, or the like, to a reaction with a metal base such as an oxide and hydroxide of an alkali metal or alkali earth metal, conversion to an alkali metal salt such as a sodium salt and potassium salt once, then substitution it with an alkali earth metal salt, or the like.
• a metal base such as an oxide and hydroxide of an alkali metal or alkali earth
• the metal salicylate-based detergent (B) for use in the lubricant oil composition of the invention includes, not only a neutral salt as obtained above, but also a basic salt obtained by heating the neutral salt and an additional excessive alkali metal or alkali earth metal salt or alkali metal or alkali earth metal base (hydroxide or oxide of alkali metal or alkali earth metal) in the presence of water, or an overbased salt obtained by reacting the neutral salt with a base such as hydroxide of alkali metal or alkali earth metal in the presence of a carbon dioxide gas, or boric acid or borate.
• a base such as hydroxide of alkali metal or alkali earth metal in the presence of a carbon dioxide gas, or boric acid or borate.
• the content of the metal salicylate-based detergent (B) is not more than 3 mass%, preferably 0.05 to 2 mass%, further preferably 0.05 to 1.5 mass%, further more preferably 0.05 to 0.8 mass%, particularly preferably 0.05 to 0.5 mass%, most preferably 0.05 to 0.25 mass% as an alkali metal or alkali earth metal amount based on the total amount of the composition.
• metal salicylate-based detergent (B) for use in the lubricant oil composition of the invention it is preferable to use one with a metal ratio of normally 1.0 to 30.
• a metal salicylate-based detergent with a metal ratio of less than 1.0 has an acid remained and is likely to have corrosive property, while a metal salicylate-based detergent with a metal ratio of not less than 30 is unstable and is likely to generate a precipitate, which are not preferable.
• the metal ratio of the metal salicylate-based detergent (B) is represented by the valence number of a metal-based element in a salicylate-based detergent x metal element content (mol%) / soap group content (mol%), the metal element means calcium, magnesium and the like, and the soap group means a salicylic acid group and the like.
• the carbon number of R 1 is preferably 10 to 40, more preferably 14 to 30, further preferably not less than 20.
• R 1 is preferably an alkyl group, more preferably a secondary alkyl group. With the carbon number of R 1 of less than 10, a sufficient friction reducing effect cannot be obtained, while with the carbon number of R 1 of more than 40, the low temperature flow property as a lubricant oil composition deteriorates, which is not preferable.
• the carbon number of an alkyl chain of a soap group is preferable to be not less than 10 as an average.
• the carbon number of an alkyl chain of a soap group is not less than 10 as an average, a sufficient friction reducing effect can be obtained.
• an overbased calcium carbonate salicylate is preferable.
• the overbased calcium carbonate salicylate is one obtained by overbasing with calcium carbonate a neutral calcium salicylate which is obtained by a method of neutralizing a hydrocarbon group substituted salicylic acid with an equivalent of a calcium base such as calcium hydroxide and calcium oxide, and the like.
• a metal-based detergent such as a sulfonate-based detergent, phenate-based detergent and carboxylate-based detergent
• the metal-based detergent other than the metal salicylate-based detergent (B) includes, for example, alkali metal sulfonate or alkali earth metal sulfonate, alkali metal phenate or alkali earth metal phenate, alkali metal carboxylate or alkali earth metal carboxylate, mixture thereof, or the like.
• an alkali metal salt or alkali earth metal salt particularly a magnesium salt and/or calcium salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound with a molecular weight of 100 to 1500, preferably 200 to 700 is preferably used, and as the alkyl aromatic sulfonic acid, a so-called petroleum sulfonic acid, synthetic sulfonic acid and the like are specifically included.
• an alkali metal salt or alkali earth metal salt particularly a magnesium salt and/or calcium salt of alkylphenol having at least one linear or branched alkyl group with a carbon number of 4 to 30, preferably 6 to 18, alkylphenol sulfide obtained by reacting this alkylphenol with an elemental sulfur, or a Mannich reaction product of alkylphenol obtained by reacting this alkylphenol with formaldehyde, and the like are preferably used.
• an alkali metal salt or alkali earth metal salt particularly a magnesium salt and/or calcium salt of an alkyl benzoic acid having at least one linear or branched alkyl group with a carbon number of 4 to 30, preferably 6 to 18, and the like are preferably used.
• metal-based detergents are normally on market and also available in a state of being diluted by a light lubricant base oil and the like. Generally, it is desirable to use one with a metal content of 1.0 to 20 mass%, preferably 2.0 to 16 mass%. Furthermore, the total base number of the metal-based detergents is normally 0 to 500 mg KOH/g, preferably 20 to 450 mg KOH/g. It should be noted that the total base number herein refers to a total base number measured by a perchloric acid method according to 7. of JIS K2501 "Petroleum Products and Lubricants - Determination of Neutralization Number".
• the lubricant oil composition of the invention is preferable to further contain an ashless dispersant.
• an ashless dispersant for use in lubricant oils can be used, and for example, a nitrogen containing compound having at least one linear or branched alkyl group or alkenyl group with a carbon number of 40 to 400 within a molecule or its derivative, a modified product of alkenylsuccinimide, benzylamine, polyamine, or the like is included.
• a nitrogen containing compound having at least one linear or branched alkyl group or alkenyl group with a carbon number of 40 to 400 within a molecule or its derivative, a modified product of alkenylsuccinimide, benzylamine, polyamine, or the like is included.
• one kind or two or more kinds optionally selected from them can be formulated.
• the carbon number of an alkyl group or alkenyl group of alkenylsuccinimide is preferably 40 to 400, more preferably 60 to 350. With the carbon number of an alkyl group or alkenyl group of less than 40, the solubility of a compound in a lubricant base oil tends to decrease, while with the carbon number of an alkyl group or alkenyl group of more than 400, the low temperature flow property of a lubricant oil composition tends to deteriorate.
• this alkyl group or alkenyl group may be linear or branched, specifically, a branched alkyl group or branched alkenyl group derived from an oligomer of olefin such as propylene, 1-butene and isobutylene or a cooligomer of ethylene and propylene, and the like are preferably included.
• the lubricant oil composition of the invention may contain either or both of monotype or bistype succinimides.
• the method for producing succinimide is not particularly limited, and it can be obtained by, for example reacting an alkylsuccinic acid or alkenylsuccinic acid obtained by reacting a compound having an alkyl group or alkenyl group with a carbon number of 40 to 400 with maleic anhydride at 100 to 200°C with a polyamine.
• a polyamine specifically, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like can be exemplified.
• R 2 represents an alkyl group or alkenyl group with a carbon number of 40 to 400, preferably 60 to 350, and p represents an integer of 1 to 5, preferably 2 to 4.
• the method for producing the above benzylamine is not particularly limited, for example, it can be obtained by reacting a polyolefin such as a propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer with a phenol into alkylphenol, and then reacting it with formaldehyde and polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine by a Mannich reaction.
• a polyolefin such as a propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer
• formaldehyde and polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine by a Mannich reaction.
• R 3 represents an alkyl group or alkenyl group with a carbon number of 40 to 400, preferably 60 to 350, and q represents an integer of 1 to 5, preferably 2 to 4.
• the method for producing the above polyamine is not particularly limited, for example, it can be obtained by chlorinating a polyolefin such as a propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer, and then reacting it with ammonia and polyamine such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
• a polyolefin such as a propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer
• the derivative of the nitrogen containing compound exemplified as one example of the ashless dispersant specifically includes, for example, a so-called acid modified compound formed by reacting the nitrogen containing compound described above with a monocarboxylic acid with a carbon number of 1 to 30 (fatty acid, etc.) and a polycarboxylic acid with a carbon number of 2 to 30 such as an oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid to partially or totally neutralize, or amidate a remaining amino group and/or imino group; a so-called boron modified compound formed by reacting the nitrogen containing compound described above with a boric acid to partially or totally neutralize, or amidate a remaining amino group and/or imino group; a sulfur modified compound formed by reacting the nitrogen containing compound described above with a sulfur compound; a modified compound formed by subjecting the nitrogen containing compound described above to two or more kinds of modifications selected from acid modification, boron modification and sulfur modification in combination; and
• a boron modified compound of alkenylsuccinimide is excellent in heat resistance property and anti-oxidizing property, and is also effective for improving base number maintaining property and high temperature detergency in the lubricant oil composition of the invention.
• an ashless dispersant When an ashless dispersant is contained in the lubricant oil composition of the invention, its content is normally 0.01 to 20 mass%, preferably 0.1 to 10 mass% based on the total amount of the lubricant oil composition. With the content of the ashless dispersant in the lubricant oil composition of less than 0.01 mass%, an effect on base number maintaining property under a high temperature is small, while with that of more than 20 mass%, the low temperature flow property of the lubricant oil composition hugely deteriorates, which are both not preferable.
• the lubricant oil composition of the invention is preferable to further contain a radical scavenger type antioxidant.
• a radical scavenger type antioxidant By containing a radical scavenger type antioxidant, anti-oxidizing property of a lubricant oil composition is further improved, and therefore base number maintaining property and high temperature detergency in the invention can further be improved.
• a phenol-based antioxidant, amine-based antioxidant, metal-based antioxidant and the like which are generally used in lubricant oils can be used. Further, the above phenol-based antioxidant and amine-based antioxidant may be used in combination.
• the radical scavenger type antioxidant When the radical scavenger type antioxidant is contained in the lubricant oil composition of the invention, its content is normally not more than 5.0 mass%, preferably not more than 3.0 mass%, further preferably not more than 2.5 mass% based on the total amount of the lubricant oil composition. When the content of the radical scavenger type antioxidant is more than 5.0 mass%, a sufficient anti-oxidizing property corresponding to the content cannot be obtained, which is not preferable.
• the content of the radical scavenger type antioxidant is, in order to further improve the base number maintaining property and the high temperature detergency in a lubricant oil deterioration process, preferably not less than 0.1 mass%, more preferably not less than 1 mass% based on the total amount of the lubricant oil composition.
• an optional additive which is generally used in lubricant oils depending on its purpose can be added.
• an additive can include, for example, an additive such as anti-wear additive, friction modifier, viscosity index improver, anti-corrosive additive, anti-rust additive, anti-emulsifying additive, metal deactivating additive, anti-foaming additive and coloring additive, and the like.
• a phosphorous compound or sulfur compound can be used as the above anti-wear additive.
• zinc carbyldithiophosphate is a representative example as the phosphorous compound, other than that, a phosphate or phosphite containing no sulfur, and a metal salt thereof are also preferably used.
• the sulfur compound includes, for example, a sulfur containing compound such as a disulfide, sulfurized olefin, sulfurized grease, metal dithiophosphate salt (zinc salt, molybdenum salt, etc.), metal dithiocarbamate salt (zinc salt, molybdenum salt, etc.), dithiophosphate ester and derivative thereof (reaction product with olefin cyclopentadiene, (methyl)methacrylic acid, propionic acid and the like; an addition product at a ⁇ position is preferable in the case of a propionic acid), trithiophosphate ester and dithiocarbamate ester, and the like.
• a sulfur containing compound such as a disulfide, sulfurized olefin, sulfurized grease, metal dithiophosphate salt (zinc salt, molybdenum salt, etc.), metal dithiocarbamate salt (zinc salt, molybdenum salt, etc.), dithiophosphate ester and derivative thereof (
• the content is preferably not more than 0.1 mass%, more preferably not more than 0.05 mass % as a sulfur conversion value, in terms of low sulfurization and long drain property.
• an optional compound which is normally used as a friction modifier for lubricant oils can be used, and for example, a molybdenum-based friction modifier such as molybdenum disulfide, molybdenum dithiocarbamate, molybdenum dithiophosphate and molybdenum amine complex can be used within a range having no influence on an exhaust gas treatment apparatus as a composition.
• a molybdenum-based friction modifier such as molybdenum disulfide, molybdenum dithiocarbamate, molybdenum dithiophosphate and molybdenum amine complex
• an ashless friction modifier such as an amine compound, fatty acid ester, fatty acid amide, fatty acid, aliphatic alcohol, aliphatic ether, hydrazide (oleyl hydrazide, etc.), semicarbazide, urea, ureide and biuret, having at least one alkyl group or alkenyl group with a carbon number of 6 to 30, particularly linear alkyl group or linear alkenyl group with a carbon number of 6 to 30 within a molecule, and the like are included.
• the content of these friction modifiers is normally 0.1 to 5 mass%.
• the above viscosity index improver specifically, includes a so-called non-dispersed type viscosity index improver such as a polymer or copolymer of one kind or two or more kinds of monomers selected from various methacrylate esters or hydrogenated product thereof, or a so-called dispersed type viscosity index improver having various methacrylate esters further containing a nitrogen compound copolymerized, a non-dispersed type or dispersed type ethylene- ⁇ -olefin copolymer (as ⁇ -olefin, propylene, 1-butene, 1-pentene, and the like can be exemplified) or hydride thereof, polyisobutylene or a hydrogenated product thereof, a hydride of a styrene-diene copolymer, a styrene-maleic anhydride ester copolymer, polyalkylstyrene, and the like.
• the molecular weight of the above viscosity index improver is preferable to be selected by considering shear stability.
• the number average molecular weight of the viscosity index improver is, for example, normally 5,000 to 1,000, 000, preferably 100,000 to 900,000 in the case of dispersed type and non-dispersed type polymethacrylates, normally 800 to 5,000, preferably 1,000 to 4,000 in the case of polyisobutylene or hydride thereof, normally 800 to 500,000, preferably 3,000 to 200,000 in the case of an ethylene- ⁇ -olefin copolymer or hydride thereof.
• a lubricant oil composition particularly excellent in shear stability can be obtained.
• one kind or two or more kinds of compounds optionally selected from the above viscosity index improvers can be contained in an optional amount.
• the content of the viscosity index improver is normally 0.1 to 20 mass% based on the lubricant oil composition.
• the above anti-corrosive additive includes, for example, benzotriazole-based, tolyltriazole-based, thiadiazole-based and imidazole-based compounds, and the like.
• the above anti-rust additive includes, for example, petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenylsuccinate ester, polyhydric alcohol ester, and the like.
• the above anti-emulsifying additive includes, for example, a polyalkylene glycol-based nonionic surfactant such as a polyoxyethylene alkylether, polyoxyethylene alkylphenylether and polyoxyethylene alkylnaphthylether, and the like.
• a polyalkylene glycol-based nonionic surfactant such as a polyoxyethylene alkylether, polyoxyethylene alkylphenylether and polyoxyethylene alkylnaphthylether, and the like.
• the above metal deactivating additive includes, for example, an imidazoline or pyrimidine derivative, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or a derivative thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamate, 2-(alkyldithio)benzoimidazole, ⁇ -(o-carboxybenzylthio)propionitrile, and the like.
• the above anti-foaming additive includes, for example, silicone, fluorosilicone, fluoroalkylether, and the like.
• the content is normally selected within a range of 0.005 to 5 mass% for the anti-corrosive additive, anti-rust additive and anti-emulsifying additive, 0.005 to 1 mass% for the metal deactivating additive, 0.0005 to 1 mass% for the anti-foaming additive.
• the friction reducing effect was evaluated by using a TE77 reciprocating friction testing machine manufactured by Phoenix Tribology (here, the test plate has a material of BS4659 and a shape of 58 mm length x 38 mm width x 4 mm thickness, and the test cylinder pin has a material of EN1A and a shape of 6 mm diameter x 16 mm length), running in at a stroke of 15 mm, 20 Hz, an oil temperature of 150°C and a load of 300 N for 30 minutes, and then measuring the friction coefficient at a stroke of 15 mm, 1 Hz, an oil temperature of 150°C and a load of 200 N.
• Lubricant oil compositions with formulations shown in Table 3 were prepared and measured for the friction coefficient.
• Base Oil A-1 mass% - - 5 15 25 50 75 100 Base Oil A-2 mass% 100 - 95 85 75 50 25 - Base Oil A-3 mass% - 100 - - - - - Salicylate B-1 mass% 1.56 1.56 1.56 1.56 1.56 1.56 1.56 1.56 1.56 1.56 Base Number (BN) mgKOH/g 5 5 5 5 5 5 5 5 Ca Amount mass% 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 %C A of Base Oil mass% 0.00 2.90 0.34 1.02 1.70 3.40 5.10 6.80 Sulfur Content of Base Oil (S) mass% 0 0.02 0.03 0.09 0.15 0.31 0.46 0.61 %C A /S of Base Oil - - 145 11 11 11 11 11 11 11 11 Friction Coefficient 200N 1Hz 0.079
• Table 3 shows the influence of the sulfur content of a base oil in Examples 1 to 6 and Comparative Examples 1 to 2. From Table 3, it is clear that when the sulfur content of a base oil is not less than 0.03 mass%, the friction coefficient becomes small.
• Lubricant oil compositions with formulations shown in Table 4 were prepared and measured for the friction coefficient.
• Table 4 shows the influence of the ratio between the aromatic content (%C A ) and the sulfur content (S) of a base oil in Examples 3, 7 and 8, and Comparative Example 3. From Table 4, it is clear that when the %C A /S of a base oil is not more than 30, the friction coefficient becomes small.
• Lubricant oil compositions with formulations shown in Table 5 were prepared and measured for the friction coefficient.
• Table 5 shows the influence of the calcium amount of a lubricant oil composition in Examples 6, 9 and 10, and Comparative Examples 1 and 4 to 7. From Examples 6, 9 and 10, and Comparative Example 4 in Table 5, it is clear that when the sulfur content of a base oil is not less than 0.03 mass%, a lubricant oil composition with a smaller calcium amount has a lower friction coefficient.
• Lubricant oil compositions with formulations shown in Table 6 were prepared and measured for the friction coefficient.
• Table 6 shows the influence of the alkyl chain length of the metal salicylate based detergent (B) in Examples 6 and 11. From Table 6, it is clear that the metal salicylate-based detergent (B) has a higher friction reducing effect with a longer alkyl chain length.
• the lubricant oil composition of the invention can be used as a general lubricant oil, can preferably be used in petrol engines, diesel engines, gas engines, and the like for two wheeled vehicles, four wheeled vehicles, power generation, cogeneration and the like, and is also useful in various engines for ships and outboard engines.
• the lubricant oil composition of the invention can also preferably be used as lubricant oils requiring friction reduction, for example, lubricant oils for drive systems such as automatic or manual transmissions, and lubricant oils such as grease, wet type brake oil, hydraulic oil, turbine oil, compressor oil, bearing oil and refrigerator oil.

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

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• 2012
  • 2012-03-30 JP JP2012081873A patent/JP2013209569A/ja active Pending
• 2013
  • 2013-03-28 KR KR20147030405A patent/KR20150003774A/ko not_active Ceased
  • 2013-03-28 IN IN8187DEN2014 patent/IN2014DN08187A/en unknown
  • 2013-03-28 WO PCT/JP2013/002139 patent/WO2013145759A1/ja not_active Ceased
  • 2013-03-28 SG SG11201406197QA patent/SG11201406197QA/en unknown
  • 2013-03-28 EP EP13770254.4A patent/EP2832840A4/de not_active Withdrawn
  • 2013-03-28 CN CN201380018039.XA patent/CN104334700A/zh active Pending

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