US20090312211A1 - Lubricant composition - Google Patents

Lubricant composition Download PDF

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US20090312211A1
US20090312211A1 US12/376,178 US37617807A US2009312211A1 US 20090312211 A1 US20090312211 A1 US 20090312211A1 US 37617807 A US37617807 A US 37617807A US 2009312211 A1 US2009312211 A1 US 2009312211A1
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lubricant
lubricant composition
mass
oil
phosphate
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US12/376,178
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Ryou Yamada
Yutaka Takakura
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Assigned to IDEMITSU KOSAN CO., LTD. reassignment IDEMITSU KOSAN CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAKAKURA, YUTAKA, YAMADA, RYOU
Publication of US20090312211A1 publication Critical patent/US20090312211A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02Polyethene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022Ethene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/43Sulfur free or low sulfur content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • the present invention relates to a lubricant composition, and more specifically, to a lubricant composition having low viscosity and has a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, thereby being particularly suitable as a lubricant for automobile transmissions or the like.
  • Energy savings that is, fuel savings in, for example, construction machines, agricultural machines and automobiles have recently become urgent matters with the advent of the need to cope with environmental issues, so an apparatus such as an engine, a transmission, a final reduction gear, a compressor, or a hydraulic system has been strongly requested to contribute to the energy savings. Accordingly, a lubricant to be used in any such apparatus has been requested to reduce the stirring resistance or frictional resistance of the apparatus to a larger extent than a conventional lubricant does.
  • a reduction in viscosity of a lubricant is one method of achieving fuel savings in each of the transmissions and the final reduction gears.
  • an automatic transmission or continuously variable transmission for automobiles has, for example, a torque converter, a wet clutch, a gear bearing mechanism, an oil pump, and a hydraulic control mechanism
  • a manual transmission or final reduction gear has a gear bearing mechanism.
  • a reduction in viscosity of a lubricant to be used in any such transmission reduces the stirring resistance and frictional resistance of, for example, each of the torque converter, the wet clutch, the gear bearing mechanism, and the oil pump, and improves the efficiency of power transmission, thereby enabling an improvement in fuel efficiency of an automobile.
  • a lubricant with its viscosity reduced is apt to be lost by evaporation particularly when used in a high-humidity environment.
  • a problem such as an increase in coefficient of friction of a film composed of the lubricant arises in association with the reduction in viscosity.
  • the lubricant has a significantly reduced fatigue life to cause seizing or the like, so a transmission or the like may undergo malfunctions.
  • a phosphorus-based extreme pressure agent is blended for improving the extreme-pressure property of a low-viscosity oil, the fatigue life of the oil remarkably deteriorates, so it is generally difficult to reduce the viscosity of the oil.
  • a composition obtained by the following procedure has been disclosed (see, for example, Patent Documents 1 and 2): a conventional transmission oil for automobiles is blended with, for example, a synthetic oil-based lubricant base oil and/or a mineral oil-based lubricant base oil, an anti-wear agent, an extreme pressure agent, a metal-based detergent, an ashless dispersant, a friction adjustor, or a viscosity index improver with the amount of any such additive optimized so that the composition to be obtained may be able to maintain various properties such as a transmission characteristic for a long time period.
  • a synthetic oil-based lubricant base oil and/or a mineral oil-based lubricant base oil an anti-wear agent, an extreme pressure agent, a metal-based detergent, an ashless dispersant, a friction adjustor, or a viscosity index improver
  • a viscosity index improver with the amount of any such additive optimized so that the composition to be obtained may be able to maintain various properties such as a
  • Patent Document 1 JP 7-268375 A
  • Patent Document 2 JP 2000-63869 A
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a lubricant composition having low viscosity and a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, and hence is particularly suitable as a lubricant for automobile transmissions.
  • the inventors of the present invention have made extensive studies with a view to developing a lubricant composition having the foregoing excellent performance. As a result, the inventors have found that the object can be achieved by blending a base oil having specific properties with an ethylene/ ⁇ -olefin copolymer having a molecular weight in a specific range at a predetermined ratio. The present invention has been completed on the basis of such finding.
  • the present invention provides:
  • a lubricant composition including: a lubricant base oil; and 0.5 to 10 mass % of (A) an ethylene/ ⁇ -olefin copolymer having a number average molecular weight of 2,800 to 8,000, in which the lubricant base oil used here has a kinematic viscosity at 100° C. of 1.5 to 40 mm 2 /s, a viscosity index of 100 or more, a pour point of ⁇ 25° C.
  • the lubricant composition according to the item (1) further including 0.01 to 2.0 mass % of (B) a phosphorus-based extreme pressure agent and/or a sulfur-based extreme pressure agent, the component (B) having a total sulfur content of 0.15 mass % or less; (3) the lubricant composition according to the item (1) or (2), further including (C) at least one kind of an additive selected from an antioxidant, another extreme pressure agent, a wear-resisting agent, an oiliness agent, a detergent, a dispersant, and a pour point depressant; and (4) the lubricant composition according to any one of the items (1) to (3), in which the lubricant composition is used as a lubricant for automobile transmissions.
  • a lubricant composition having low viscosity and a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, and hence is particularly suitable as a lubricant for automobile transmissions or the like.
  • a base oil having the following properties.
  • the base oil must have a kinematic viscosity at 100° C. in the range of 1.5 to 40 mm 2 /s.
  • the kinematic viscosity is 1.5 mm 2 /s or more, the evaporation loss of the lubricant composition is small, so an improving effect on fuel efficiency can be obtained.
  • the kinematic viscosity is 40 mm 2 /s or less, a power loss due to the viscous resistance of the lubricant composition does not become very large, so the improving effect on fuel efficiency can be similarly obtained.
  • the kinematic viscosity is preferably 2 to 25 mm 2 /s, or particularly preferably 2 to 10 mm 2 /s.
  • the base oil must have a viscosity index of 100 or more and a pour point of ⁇ 25° C. or lower.
  • the viscosity index is 100 or more, a change in viscosity of the lubricant composition due to a temperature change is small.
  • the viscosity index is preferably 105 or more, or more preferably 110 or more.
  • the pour point is ⁇ 25° C. or lower, the lubricant composition to be obtained has sufficient fluidity even in a low-temperature environment.
  • the pour point is preferably ⁇ 30° C. or lower, or more preferably ⁇ 40° C. or lower.
  • kinematic viscosity and the viscosity index are each a value measured in accordance with JIS K 2283, and the pour point is a value measured in accordance with JIS K 2265.
  • the base oil must have a sulfur content of 0.01 mass % or less.
  • the sulfur content is 0.01 mass % or less, the oxidation stability of the lubricant composition to be obtained becomes good. It should be noted that the sulfur content is a value measured in accordance with JIS K 2541.
  • the kind of the base oil is not particularly limited, and each of a mineral oil and a synthetic oil can be used as the base oil.
  • any one of the various conventionally known mineral oils can be used as the mineral oil, and examples of the mineral oil include a paraffin base mineral oil, an intermediate base mineral oil, and a naphthene base mineral oil.
  • Specific examples of the mineral oil include a light neutral oil, medium neutral oil, heavy neutral oil, or bright stock obtained by solvent refining, hydrogenation refining, or the like, and a mineral oil obtained by the isomerization of a wax.
  • any one of the various conventionally known synthetic oils can be also used as the synthetic oil, and examples of the synthetic oil include poly ⁇ -olefin, polybutene, polyol ester, dibasic acid ester, phosphate, polyphenyl ether, alkyl benzene, alkyl naphthalene, polyoxyalkylene glycol, neopentyl glycol, silicone oil, trimethylol propane, and pentaerythritol, and further include hindered ester.
  • Those base oils may be used alone or in combination of two or more kinds.
  • a mineral oil and a synthetic oil may be used in combination.
  • the lubricant composition of the present invention has the feature of containing the base oil having the foregoing properties and 0.5 to 10 mass % of (A) an ethylene/ ⁇ -olefin copolymer having a number average molecular weight of 2,800 to 8,000.
  • the ethylene/ ⁇ -olefin copolymer to be used as the component (A) in the lubricant composition of the present invention has a number average molecular weight in the range of 2,800 to 8,000.
  • the number average molecular weight is preferably 3,000 to 7,000 from the viewpoints of the improving effect on the viscosity index and the impartment of good shear stability.
  • the number average molecular weight is a value measured by vapor pressure osmometry.
  • ⁇ -olefin constituting the ethylene/ ⁇ -olefin copolymer
  • an ethylene/ ⁇ -olefin copolymer having carbon atoms of preferably 3 to 20, or more preferably 3 to 10 is used.
  • the ⁇ -olefin include propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, and 1-decene.
  • One kind of the ⁇ -olefin may be used or two or more kinds of the ⁇ -olefins may be used in combination. Particularly suitable is propylene in terms of the performance of the composition.
  • the content of an ethylene unit in the ethylene/ ⁇ -olefin copolymer is preferably 15 to 85 mol %, or more preferably 20 to 80 mol % in terms of the performance of the composition.
  • the manner in which the ethylene unit and the ⁇ -olefin are copolymerized is not particularly limited, and the copolymer may be either a random copolymer or a block copolymer.
  • the ethylene/ ⁇ -olefin copolymer may be used as the component (A), or two or more kinds of the ethylene/ ⁇ -olefin copolymers may be used in combination as the component (A).
  • the component (A) is a component to be blended in to the base oil for providing the lubricant composition of the present invention with low viscosity, excellent low-temperature fluidity and oxidation stability, and a long metal fatigue life.
  • the content of the component (A) is 0.5 to 10 mass %, preferably 0.5 to 6 mass %, or more preferably 0.5 to 4.5 mass % with respect to the total amount of the composition from the viewpoints of the foregoing properties.
  • a phosphorus-based extreme pressure agent and/or a sulfur-based extreme pressure agent can be further incorporated as a component (B) into the lubricant composition of the present invention.
  • Examples of the phosphorus-based extreme pressure agent include phosphate, acidic phosphate, acidic phosphate amine salt, phosphite, acidic phosphite, and acidic phosphite amine salt.
  • triaryl phosphate there are given triaryl phosphate, trialkyl phosphate, trialkylaryl phosphate, triarylalkyl phosphate, and trialkenyl phosphate
  • examples thereof include triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate, ethylphenyldiphenyl phosphate, di(ethylphenyl)phenyl phosphate, propylphenyldiphenyl phosphate, di(propylphenyl)phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, di(butylphenyl)
  • acidic phosphate examples include di-2-ethylhexyl acid phosphate, didecylacid phosphate, didodecyl acid phosphate (dilauryl acid phosphate), tridecyl acid phosphate, dioctadecyl acid phosphate (distearyl acid phosphate), and di-9-octadecenylacidphosphate (dioleylacidphosphate).
  • phosphite examples include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl)phosphite, tri(2-ethylhexyl)phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl phosphite.
  • acidic phosphite examples include di-2-ethylhexyl hydrogen phosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauryl hydrogen phosphite), dioctadecyl hydrogen phosphite (distearyl hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite), and diphenyl hydrogen phosphite.
  • acidic phosphate amine salt and the acidic phosphite amine salt salts formed of the above-mentioned acidic phosphates and acidic phosphites and the following amines are exemplified.
  • amines a monosubstituted amine, a disubstituted amine, or a trisubstituted amine may be used.
  • Examples of the monosubstituted amine include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, andbenzylamine.
  • disubstituted amine examples include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanol.
  • trisubstituted amine examples include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl propanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triethanolamine, and tripropanolamine.
  • acidic phosphate amine salt a salt formed of the acidic monophosphate and the above-mentioned amine such as monomethyl hydrogen phosphate, monoethyl hydrogen phosphate, monopropyl hydrogen phosphate, monobutyl hydrogen phosphate, or mono-2-ethylhexyl hydrogen phosphate can be used.
  • one kind of the phosphate-based compound may be used or two or more kinds of the phosphate-based compounds may be used in combination.
  • the sulfur-based extreme pressure agent has only to have the following characteristics: the agent has a sulfur atom in any one of its molecules, and is dissolved or uniformly dispersed in the lubricant base oil so as to be capable of exerting extreme-pressure property or an excellent friction characteristic.
  • sulfur-based extreme pressure agent having such characteristics include sulfurized fats and oils, a sulfurized fatty acid, a sulfurized ester, a sulfurized olefin, dihydrocarbyl polysulfide, a thiadiazole compound, a thiophosphoric acid ester (thiophosphite or thiophosphate), an alkylthiocarbamoyl compound, a thiocarbamate compound, a thioterpene compound, and a dialkyl thiodipropionate compound.
  • sulfurized fats and oils examples include sulfurized fats and oils, a sulfurized fatty acid, a sulfurized ester, a sulfurized olefin, dihydrocarbyl polysulfide, a thiadiazole compound, a thiophosphoric acid ester (thiophosphite or thiophosphate), an alkylthiocarbamoyl compound, a thiocarbamate compound, a thi
  • the sulfurized fats and oils can be obtained by causing sulfur or a sulfur-containing compound and fats and oils (such as a lard oil, a whale oil, a vegetable oil, and a fish oil) to react with each other, and the sulfur content of each of the sulfurized fats and oils, which is not particularly limited, is suitably 5 to 30 mass % in ordinary cases.
  • Specific examples of such fats and oils include a sulfurized lard, a sulfurized rapeseed oil, a sulfurized castor oil, a sulfurized soybean oil, and a sulfurized rice bran oil.
  • the sulfurized fatty acid is, for example, a sulfurized oleic acid.
  • the sulfurized ester include sulfurized methyl oleate and sulfurized rice bran fatty acid octyl.
  • the sulfurized olefin is, for example, a compound represented by the following general formula (I):
  • R 1 represents an alkenyl group having 2 to 15 carbon atoms
  • R 2 represents an alkyl or alkenyl group having 2 to 15 carbon atoms
  • q represents an integer of 1 to 8.
  • the compound is obtained by causing an olefin having 2 to 15 carbon atoms or a dimer, trimer, or tetramer of the olefin and a sulfurizing agent such as sulfur or sulfur chloride to react with each other, and the olefin is preferably, for example, propylene, isobutene, or diisobutene.
  • the dihydrocarvyl polysulfide is, for example, a compound represented by the following general formula (II):
  • 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, an alkyl aryl group having 7 to 20 carbon atoms, or an aryl alkyl group having 7 to 20 carbon atoms, which may be identical to or different from each other; and r represents an integer of 1 to 8. when both R 3 and R 4 are alkyl groups, the compound is referred to as sulfurized alkyl.
  • Examples of the dihydrocarbyl polysulfide represented by the general formula (II) preferably include dibenzyl polysulfide, various dinonyl polysulfides, various didodecyl polysulfides, various dibutyl polysulfides, various dioctyl polysulfides, diphenyl polysulfide, and dicyclohexyl polysulfide.
  • Examples of the thiadiazole compound preferably include
  • thiophosphoric acid ester examples include alkyl trithiophosphite, aryl or alkyl aryl thiophosphate, and zinc dilauryl dithiophosphate. Particularly preferred are lauryl thiophosphite and triphenyl tiophosphate.
  • alkyl thiocarbamoyl compound examples include bis(dimethyl thiocarbamoyl)monosulfide, bis(dibutyl thiocarbamoyl)monosulfide, bis(dimethyl thiocarbamoyl)disulfide, bis(dibutyl thiocarbamoyl)disulfide, bis(diamyl thiocarbamoyl)disulfide, and bis(dioctyl thiocarbamoyl)disulfide.
  • the thiocarbamate compound is, for example, a zinc dialkyldithiocarbamate
  • the thioterpene compound is, for example, a product of a reaction between phosphorus pentasulfide and pinene
  • examples of the dialkyl thiodipropionate compound include dilauryl thiodipropionate and distearyl thiodipropionate.
  • the thiadiazole compound or benzyl sulfide is suitable in terms of, for example, extreme-pressure property, a friction characteristic, and thermal oxidation stability.
  • sulfur-based extreme pressure agents may be used alone, or two or more kinds of them may be used in combination.
  • the phosphorus-based extreme pressure agent may be used as the component (B)
  • only the sulfur-based extreme pressure agent may be used as the component (B)
  • the phosphorus-based extreme pressure agent and the sulfur-based extreme pressure agent may be used in combination as the component (B).
  • the content of the component (B) is typically about 0.01 to 2.0 mass %, or preferably 0.05 to 1.5 mass % with respect to the total amount of the lubricant composition in terms of, for example, a balance between the effect and economical efficiency of the component as an extreme pressure agent.
  • the amount in which the agent is blended is preferably adjusted so that the total sulfur content in the composition may be preferably 0.15 mass % or less, or more preferably 0.10 mass % or less.
  • At least one kind of an additive selected from an antioxidant, another extreme pressure agent, a wear-resisting agent, an oiliness agent, a detergent dispersant, and a pour point depressant can be further incorporated as a component (C) into the lubricant composition of the present invention.
  • antioxidants examples include an amine-based antioxidants, phenol-based antioxidants, and a sulfur-based antioxidants.
  • amine-based antioxidants examples include: monoalkyldiphenylamine-based compounds such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamine-based compounds such as 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine, and 4,4′-dinonyldiphenylamine; polyalkyldiphenylamine-based compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; and naphthylamine-based compounds such as ⁇ -naphthylamine, phenyl- ⁇ -
  • phenol-based antioxidant examples include monophenol-based compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; and diphenol-based compounds such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and 2,2′-methylenebis(4-ethyl-6-tert-butylphenol).
  • sulfur-based antioxidant examples include phenothiazine, pentaerythritol-tetrakis(3-laurylthiopropionate), bis(3,5-tert-butyl-4-hydroxybenzyl)sulfide, thiodiethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-methylamino)phenol.
  • antioxidants may be used alone or two or more of them may be used in combination. Further, the blending amounts of those antioxidants are typically in the range of 0.01 to 10 mass %, or preferably in a range of 0.03 to 5 mass % on the basis of the total amount of the lubricant composition.
  • organic metal compounds such as zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), oxymolybdenum organo phosphorodithioate sulfide (MODTP), and oxymolybdenum dithiocarbamate sulfide (MDTC).
  • ZnDTP zinc dithiophosphate
  • ZnDTC zinc dithiocarbamate
  • MODTP oxymolybdenum organo phosphorodithioate sulfide
  • MDTC oxymolybdenum dithiocarbamate sulfide
  • the blending amount of those is typically 0.05 to 5 mass %, or preferably 0.1 to 3 mass % based on the total amount of lubricant composition.
  • oiliness agents including aliphatic saturated and unsaturated monocarboxylic acids such as stearic acids and oleic acids; polymerized fatty acids such as dimer acids and hydrogenated dimer acids; hydroxy fatty acids such as ricinoleic acids and 12-hydroxystearic acids; aliphatic saturated and unsaturated monohydric alcohols such as lauryl alcohol and oleyl alcohol; aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine; and aliphatic saturated andunsaturated monocarboxylic acid amides such as lauric acid amide and oleamide.
  • aliphatic saturated and unsaturated monocarboxylic acids such as stearic acids and oleic acids
  • polymerized fatty acids such as dimer acids and hydrogenated dimer acids
  • hydroxy fatty acids such as ricinoleic acids and 12-hydroxystearic acids
  • aliphatic saturated and unsaturated monohydric alcohols such as lauryl alcohol
  • the preferable blending amount of those oiliness agents is typically in a range of 0.01 to 10 mass %, or particularly preferably in a range of 0.1 to 5 mass % based on the total amount of lubricant composition.
  • detergents and the dispersants include: ashless dispersants such as succinimides, boron-containing succinimides, benzylamines, boron-containing benzylamines, succinates, and monovalant or bivalent carboxylic amides typified by fatty acids or succinic acids; and metal-based detergents such as neutral metal sulfonate, neutral metal phenate, neutral metal salicylate, neutral metal phosphonate, basic sulfonate, basic phenate, basic salicylate, over-based sulfonate, over-based salicylate, and over-based phosphonate.
  • the blending amount of those detergent dispersants is typically 0.1 to 20 mass %, or preferably 0.5 to 10 mass % based on the total amount of lubricant composition.
  • a polymethacrylate having a weight average molecular weight of about 50,000 to 150,000 can be used as the pour point depressant.
  • An additive except those described above such as a rust inhibitor, a metal deactivator, a defoaming agent, or a surfactant can be incorporated into the lubricant composition of the present invention as desired.
  • rust inhibitor alkenyl succinic acid and partial esters thereof
  • metal corrosion inhibitor benzotriazole-based, benzimidazole-based, benzothiazole-based, and thiadiazole-based ones
  • metal deactivator benzotriazole, benzotriazole derivatives, benzothiazole, benzothiazole derivatives, triazole, triazole derivatives, dithiocarbamate, dithiocarbamate derivatives, imidazole, and imidazole derivatives.
  • defoaming agent dimethyl polysiloxane and polyacrylate
  • surfactant polyoxyethylene alkylphenyl ether.
  • the lubricant composition of the present invention has, for example, the following characteristics: the lubricant composition has low viscosity, is excellent in low-temperature fluidity and oxidation stability, and has a long metal fatigue life. Accordingly, the lubricant composition is suitably used as, for example, an oil for transmissions, power steering oil, shock absorber oil, or engine oil in automobiles, or a gear oil, hydraulic oil, or bearing oil for automobiles and industries; the lubricant composition is particularly suitable as an oil for transmissions such as an automatic transmission, a manual transmission, and a continuously variable transmission in automobiles.
  • a Brookfield viscosity at ⁇ 40° C. was measured in accordance with ASTM D 2983.
  • a fatigue life was measured with a four-ball rolling fatigue tester in the following manner.
  • a time period required for flaking to occur in the test piece was defined as a fatigue life, and an L50 (average) was calculated from the results of the test performed six times.
  • a test oil was forcedly deteriorated in an ISOT test (1500° C.) in accordance with JIS K 2514.
  • the percentage by which the viscosity changed (40° C., 100° C.), an increase in total acid number, a base number, the amount of n-heptane insoluble matter, and an increase in copper element were measured 144 hours after the deterioration.
  • Table 1 shows the properties of the base oils.
  • a product available under the trade name “Lucant HC600” from Mitsui Chemicals the product having a number average molecular weight of 2,600, a kinematic viscosity at 100° C. of 600 mm 2 /s, a viscosity index of 240, and a sulfur content of less than 0.1 mass %
  • a product available under the trade name “Lucant HC2000” from Mitsui Chemicals the product having a number average molecular weight of 3,700, a kinematic viscosity at 100° C. of 2,000 mm 2 /s, a viscosity index of 300, and a sulfur content of less than 0.1 mass % Ethylene/ ⁇ -olefin copolymer III (including diluent oil having a concentration of 50 mass %)
  • a product available under the trade name “Lucant HS4010M” from Mitsui Chemicals the product having a number average molecular weight of 6,600, a kinematic viscosity at 100° C. of 2,000 mm 2 /s, a viscosity index of 335, and a sulfur content of less than 0.1 mass %
  • a product available under the trade name “Infineum T4261” from Infineum the product containing a phosphorus-based extreme pressure agent, a sulfur-based extreme pressure agent, a detergent dispersant, a friction adjustor, and an antioxidant
  • Lubricant compositions each having the composition shown in Table 2 were prepared, and were each evaluated for physical properties except oxidation stability. Table 2 shows the results.
  • Example 1 The lubricant compositions of Example 1 and Comparative Example were each evaluated for oxidation stability. Table 3 shows the results.
  • each of the lubricant compositions of the present invention has a low-temperature viscosity ( ⁇ 40° C.) of less than 10,000 and a fatigue life [L50] in excess of 150 minutes, so each of them has good low-temperature fluidity and a long metal fatigue life.
  • each of the lubricant compositions of Comparative Examples 1 to 4 and Comparative Example 6 has a fatigue life [L50] of less than 150 minutes, so each of them has a short metal fatigue life.
  • each of the lubricant compositions of Comparative Examples 1, 4, and 6 has a low-temperature viscosity ( ⁇ 40° C.) in excess of 10,000, so each of them is poor in low-temperature fluidity.
  • the lubricant composition of Comparative Example 5 has a fatigue life [L50] in excess of 150 minutes, so the lubricant composition has a long metal fatigue life.
  • the lubricant composition has extremely bad low-temperature fluidity.
  • the lubricant composition is inferior in oxidation stability to the lubricant composition of Example 1.
  • the lubricant composition of the present invention has the following characteristics: the lubricant composition has low viscosity, is excellent in low-temperature fluidity and oxidation stability, and has a long metal fatigue life. Accordingly, the lubricant composition is suitably used as, for example, an oil for transmissions, power steering oil, shock absorber oil, or engine oil in automobiles, or a gear oil, hydraulic oil, or bearing oil for automobiles and industries.

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Abstract

Provided is a lubricant composition containing a lubricant base oil and 0.5 to 10 mass % of (A) an ethylene/α-olefin copolymer having a number average molecular weight of 2,800 to 8,000, in which the lubricant base oil used here has a kinematic viscosity at 100° C. of 1.5 to 40 mm2/s, a viscosity index of 100 or more, a pour point of −25° C. or lower, and a sulfur content of 0.01 mass % or less, and the lubricant composition has low viscosity and a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, thereby being particularly suitable as a lubricant for automobile transmissions or the like.

Description

    TECHNICAL FIELD
  • The present invention relates to a lubricant composition, and more specifically, to a lubricant composition having low viscosity and has a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, thereby being particularly suitable as a lubricant for automobile transmissions or the like.
  • BACKGROUND ART
  • Energy savings, that is, fuel savings in, for example, construction machines, agricultural machines and automobiles have recently become urgent matters with the advent of the need to cope with environmental issues, so an apparatus such as an engine, a transmission, a final reduction gear, a compressor, or a hydraulic system has been strongly requested to contribute to the energy savings. Accordingly, a lubricant to be used in any such apparatus has been requested to reduce the stirring resistance or frictional resistance of the apparatus to a larger extent than a conventional lubricant does.
  • For example, a reduction in viscosity of a lubricant is one method of achieving fuel savings in each of the transmissions and the final reduction gears. Of the transmissions, an automatic transmission or continuously variable transmission for automobiles has, for example, a torque converter, a wet clutch, a gear bearing mechanism, an oil pump, and a hydraulic control mechanism, and a manual transmission or final reduction gear has a gear bearing mechanism. A reduction in viscosity of a lubricant to be used in any such transmission reduces the stirring resistance and frictional resistance of, for example, each of the torque converter, the wet clutch, the gear bearing mechanism, and the oil pump, and improves the efficiency of power transmission, thereby enabling an improvement in fuel efficiency of an automobile.
  • However, a lubricant with its viscosity reduced is apt to be lost by evaporation particularly when used in a high-humidity environment. Moreover, a problem such as an increase in coefficient of friction of a film composed of the lubricant arises in association with the reduction in viscosity. As a result, the lubricant has a significantly reduced fatigue life to cause seizing or the like, so a transmission or the like may undergo malfunctions. In particular, when a phosphorus-based extreme pressure agent is blended for improving the extreme-pressure property of a low-viscosity oil, the fatigue life of the oil remarkably deteriorates, so it is generally difficult to reduce the viscosity of the oil.
  • For example, a composition obtained by the following procedure has been disclosed (see, for example, Patent Documents 1 and 2): a conventional transmission oil for automobiles is blended with, for example, a synthetic oil-based lubricant base oil and/or a mineral oil-based lubricant base oil, an anti-wear agent, an extreme pressure agent, a metal-based detergent, an ashless dispersant, a friction adjustor, or a viscosity index improver with the amount of any such additive optimized so that the composition to be obtained may be able to maintain various properties such as a transmission characteristic for a long time period. However, no investigation has been conducted on an influence of any such composition on the fatigue life of a lubricant when the viscosity of the lubricant is reduced.
  • Patent Document 1: JP 7-268375 A
  • Patent Document 2: JP 2000-63869 A
  • DISCLOSURE OF THE INVENTION Problems to be solved by the Invention
  • The present invention has been made in view of such circumstances, and an object of the present invention is to provide a lubricant composition having low viscosity and a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, and hence is particularly suitable as a lubricant for automobile transmissions.
  • Means for Solving the Problems
  • The inventors of the present invention have made extensive studies with a view to developing a lubricant composition having the foregoing excellent performance. As a result, the inventors have found that the object can be achieved by blending a base oil having specific properties with an ethylene/α-olefin copolymer having a molecular weight in a specific range at a predetermined ratio. The present invention has been completed on the basis of such finding.
  • That is, the present invention provides:
  • (1) a lubricant composition including: a lubricant base oil; and 0.5 to 10 mass % of (A) an ethylene/α-olefin copolymer having a number average molecular weight of 2,800 to 8,000, in which the lubricant base oil used here has a kinematic viscosity at 100° C. of 1.5 to 40 mm2/s, a viscosity index of 100 or more, a pour point of −25° C. or lower, and a sulfur content of 0.01 mass % or less;
    (2) the lubricant composition according to the item (1), further including 0.01 to 2.0 mass % of (B) a phosphorus-based extreme pressure agent and/or a sulfur-based extreme pressure agent, the component (B) having a total sulfur content of 0.15 mass % or less;
    (3) the lubricant composition according to the item (1) or (2), further including (C) at least one kind of an additive selected from an antioxidant, another extreme pressure agent, a wear-resisting agent, an oiliness agent, a detergent, a dispersant, and a pour point depressant; and
    (4) the lubricant composition according to any one of the items (1) to (3), in which the lubricant composition is used as a lubricant for automobile transmissions.
  • According to the present invention, there can be provided a lubricant composition having low viscosity and a long metal fatigue life, while being excellent in low-temperature fluidity and oxidation stability, and hence is particularly suitable as a lubricant for automobile transmissions or the like.
  • BEST MODE FOR CARRYING OUT THE INVENTION
  • In a lubricant composition of the present invention, there is used a base oil having the following properties.
  • The base oil must have a kinematic viscosity at 100° C. in the range of 1.5 to 40 mm2/s. When the kinematic viscosity is 1.5 mm2/s or more, the evaporation loss of the lubricant composition is small, so an improving effect on fuel efficiency can be obtained. Meanwhile, when the kinematic viscosity is 40 mm2/s or less, a power loss due to the viscous resistance of the lubricant composition does not become very large, so the improving effect on fuel efficiency can be similarly obtained. The kinematic viscosity is preferably 2 to 25 mm2/s, or particularly preferably 2 to 10 mm2/s.
  • The base oil must have a viscosity index of 100 or more and a pour point of −25° C. or lower. When the viscosity index is 100 or more, a change in viscosity of the lubricant composition due to a temperature change is small. The viscosity index is preferably 105 or more, or more preferably 110 or more. In addition, when the pour point is −25° C. or lower, the lubricant composition to be obtained has sufficient fluidity even in a low-temperature environment. The pour point is preferably −30° C. or lower, or more preferably −40° C. or lower.
  • It should be noted that the kinematic viscosity and the viscosity index are each a value measured in accordance with JIS K 2283, and the pour point is a value measured in accordance with JIS K 2265.
  • In addition, the base oil must have a sulfur content of 0.01 mass % or less. When the sulfur content is 0.01 mass % or less, the oxidation stability of the lubricant composition to be obtained becomes good. It should be noted that the sulfur content is a value measured in accordance with JIS K 2541.
  • The kind of the base oil is not particularly limited, and each of a mineral oil and a synthetic oil can be used as the base oil. Here, any one of the various conventionally known mineral oils can be used as the mineral oil, and examples of the mineral oil include a paraffin base mineral oil, an intermediate base mineral oil, and a naphthene base mineral oil. Specific examples of the mineral oil include a light neutral oil, medium neutral oil, heavy neutral oil, or bright stock obtained by solvent refining, hydrogenation refining, or the like, and a mineral oil obtained by the isomerization of a wax.
  • In addition, any one of the various conventionally known synthetic oils can be also used as the synthetic oil, and examples of the synthetic oil include poly α-olefin, polybutene, polyol ester, dibasic acid ester, phosphate, polyphenyl ether, alkyl benzene, alkyl naphthalene, polyoxyalkylene glycol, neopentyl glycol, silicone oil, trimethylol propane, and pentaerythritol, and further include hindered ester. Those base oils may be used alone or in combination of two or more kinds. A mineral oil and a synthetic oil may be used in combination.
  • The lubricant composition of the present invention has the feature of containing the base oil having the foregoing properties and 0.5 to 10 mass % of (A) an ethylene/α-olefin copolymer having a number average molecular weight of 2,800 to 8,000.
  • The ethylene/α-olefin copolymer to be used as the component (A) in the lubricant composition of the present invention has a number average molecular weight in the range of 2,800 to 8,000. When the number average molecular weight is −2,800 or more, an improving effect on the viscosity index of the lubricant composition to be obtained is exerted. Meanwhile, when the number average molecular weight is 8,000 or less, the shear stability of the lubricant composition to be obtained becomes good. The number average molecular weight is preferably 3,000 to 7,000 from the viewpoints of the improving effect on the viscosity index and the impartment of good shear stability.
  • It should be noted that the number average molecular weight is a value measured by vapor pressure osmometry.
  • As the α-olefin constituting the ethylene/α-olefin copolymer, an ethylene/α-olefin copolymer having carbon atoms of preferably 3 to 20, or more preferably 3 to 10 is used. Examples of the α-olefin include propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, and 1-decene. One kind of the α-olefin may be used or two or more kinds of the α-olefins may be used in combination. Particularly suitable is propylene in terms of the performance of the composition.
  • In addition, the content of an ethylene unit in the ethylene/α-olefin copolymer is preferably 15 to 85 mol %, or more preferably 20 to 80 mol % in terms of the performance of the composition. The manner in which the ethylene unit and the α-olefin are copolymerized is not particularly limited, and the copolymer may be either a random copolymer or a block copolymer.
  • In the lubricant composition of the present invention, one kind of the ethylene/α-olefin copolymer may be used as the component (A), or two or more kinds of the ethylene/α-olefin copolymers may be used in combination as the component (A). The component (A) is a component to be blended in to the base oil for providing the lubricant composition of the present invention with low viscosity, excellent low-temperature fluidity and oxidation stability, and a long metal fatigue life.
  • Therefore, the content of the component (A) is 0.5 to 10 mass %, preferably 0.5 to 6 mass %, or more preferably 0.5 to 4.5 mass % with respect to the total amount of the composition from the viewpoints of the foregoing properties.
  • A phosphorus-based extreme pressure agent and/or a sulfur-based extreme pressure agent can be further incorporated as a component (B) into the lubricant composition of the present invention.
  • Examples of the phosphorus-based extreme pressure agent include phosphate, acidic phosphate, acidic phosphate amine salt, phosphite, acidic phosphite, and acidic phosphite amine salt.
  • As the triphosphate, there are given triaryl phosphate, trialkyl phosphate, trialkylaryl phosphate, triarylalkyl phosphate, and trialkenyl phosphate, and examples thereof include triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate, ethylphenyldiphenyl phosphate, di(ethylphenyl)phenyl phosphate, propylphenyldiphenyl phosphate, di(propylphenyl)phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, di(butylphenyl)phenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri(2-ethylhexyl)phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, and trioleyl phosphate.
  • Examples of the acidic phosphate include di-2-ethylhexyl acid phosphate, didecylacid phosphate, didodecyl acid phosphate (dilauryl acid phosphate), tridecyl acid phosphate, dioctadecyl acid phosphate (distearyl acid phosphate), and di-9-octadecenylacidphosphate (dioleylacidphosphate). Examples of the phosphite include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl)phosphite, tri(2-ethylhexyl)phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl phosphite.
  • Examples of the acidic phosphite include di-2-ethylhexyl hydrogen phosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauryl hydrogen phosphite), dioctadecyl hydrogen phosphite (distearyl hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite), and diphenyl hydrogen phosphite.
  • As the acidic phosphate amine salt and the acidic phosphite amine salt, salts formed of the above-mentioned acidic phosphates and acidic phosphites and the following amines are exemplified. As the amines, a monosubstituted amine, a disubstituted amine, or a trisubstituted amine may be used.
  • Examples of the monosubstituted amine include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, andbenzylamine. Examples of the disubstituted amine include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanol. Examples of the trisubstituted amine include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl propanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triethanolamine, and tripropanolamine.
  • In addition, as the acidic phosphate amine salt, a salt formed of the acidic monophosphate and the above-mentioned amine such as monomethyl hydrogen phosphate, monoethyl hydrogen phosphate, monopropyl hydrogen phosphate, monobutyl hydrogen phosphate, or mono-2-ethylhexyl hydrogen phosphate can be used.
  • In the present invention, one kind of the phosphate-based compound may be used or two or more kinds of the phosphate-based compounds may be used in combination.
  • Meanwhile, the sulfur-based extreme pressure agent has only to have the following characteristics: the agent has a sulfur atom in any one of its molecules, and is dissolved or uniformly dispersed in the lubricant base oil so as to be capable of exerting extreme-pressure property or an excellent friction characteristic. Examples of the sulfur-based extreme pressure agent having such characteristics include sulfurized fats and oils, a sulfurized fatty acid, a sulfurized ester, a sulfurized olefin, dihydrocarbyl polysulfide, a thiadiazole compound, a thiophosphoric acid ester (thiophosphite or thiophosphate), an alkylthiocarbamoyl compound, a thiocarbamate compound, a thioterpene compound, and a dialkyl thiodipropionate compound. Here, the sulfurized fats and oils can be obtained by causing sulfur or a sulfur-containing compound and fats and oils (such as a lard oil, a whale oil, a vegetable oil, and a fish oil) to react with each other, and the sulfur content of each of the sulfurized fats and oils, which is not particularly limited, is suitably 5 to 30 mass % in ordinary cases. Specific examples of such fats and oils include a sulfurized lard, a sulfurized rapeseed oil, a sulfurized castor oil, a sulfurized soybean oil, and a sulfurized rice bran oil. The sulfurized fatty acid is, for example, a sulfurized oleic acid. Examples of the sulfurized ester include sulfurized methyl oleate and sulfurized rice bran fatty acid octyl.
  • The sulfurized olefin is, for example, a compound represented by the following general formula (I):

  • R1—Sq—R2  (I)
  • where: R1 represents an alkenyl group having 2 to 15 carbon atoms; R2 represents an alkyl or alkenyl group having 2 to 15 carbon atoms; and q represents an integer of 1 to 8.
  • The compound is obtained by causing an olefin having 2 to 15 carbon atoms or a dimer, trimer, or tetramer of the olefin and a sulfurizing agent such as sulfur or sulfur chloride to react with each other, and the olefin is preferably, for example, propylene, isobutene, or diisobutene.
  • The dihydrocarvyl polysulfide is, for example, a compound represented by the following general formula (II):

  • R3—Sr—R4  (II)
  • where R3 and R4 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, an alkyl aryl group having 7 to 20 carbon atoms, or an aryl alkyl group having 7 to 20 carbon atoms, which may be identical to or different from each other; and r represents an integer of 1 to 8.
    when both R3 and R4 are alkyl groups, the compound is referred to as sulfurized alkyl.
  • Examples of the dihydrocarbyl polysulfide represented by the general formula (II) preferably include dibenzyl polysulfide, various dinonyl polysulfides, various didodecyl polysulfides, various dibutyl polysulfides, various dioctyl polysulfides, diphenyl polysulfide, and dicyclohexyl polysulfide.
  • Examples of the thiadiazole compound preferably 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,
    • 3,6-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-thiadiazole,
    • 4,5-bis(n-octyldithio)-1,3,4-thiadiazole,
    • 4,5-bis(n-nonyldithio)-1,2,3-thiadiazole, and
    • 4,5-bis(1,1,3,3-tetramethylbutyldithio)-1,2,3-thiadiazole.
  • Examples of the thiophosphoric acid ester include alkyl trithiophosphite, aryl or alkyl aryl thiophosphate, and zinc dilauryl dithiophosphate. Particularly preferred are lauryl thiophosphite and triphenyl tiophosphate.
  • Examples of the alkyl thiocarbamoyl compound include bis(dimethyl thiocarbamoyl)monosulfide, bis(dibutyl thiocarbamoyl)monosulfide, bis(dimethyl thiocarbamoyl)disulfide, bis(dibutyl thiocarbamoyl)disulfide, bis(diamyl thiocarbamoyl)disulfide, and bis(dioctyl thiocarbamoyl)disulfide.
  • Further, the thiocarbamate compound is, for example, a zinc dialkyldithiocarbamate, the thioterpene compound is, for example, a product of a reaction between phosphorus pentasulfide and pinene, and examples of the dialkyl thiodipropionate compound include dilauryl thiodipropionate and distearyl thiodipropionate. Of those, the thiadiazole compound or benzyl sulfide is suitable in terms of, for example, extreme-pressure property, a friction characteristic, and thermal oxidation stability.
  • One kind of those sulfur-based extreme pressure agents may be used alone, or two or more kinds of them may be used in combination.
  • In the lubricant composition of the present invention, only the phosphorus-based extreme pressure agent may be used as the component (B), only the sulfur-based extreme pressure agent may be used as the component (B), or the phosphorus-based extreme pressure agent and the sulfur-based extreme pressure agent may be used in combination as the component (B).
  • The content of the component (B) is typically about 0.01 to 2.0 mass %, or preferably 0.05 to 1.5 mass % with respect to the total amount of the lubricant composition in terms of, for example, a balance between the effect and economical efficiency of the component as an extreme pressure agent.
  • It should be noted that, when the sulfur-based extreme pressure agent is used, from the viewpoint of corrosion prevention, the amount in which the agent is blended is preferably adjusted so that the total sulfur content in the composition may be preferably 0.15 mass % or less, or more preferably 0.10 mass % or less.
  • At least one kind of an additive selected from an antioxidant, another extreme pressure agent, a wear-resisting agent, an oiliness agent, a detergent dispersant, and a pour point depressant can be further incorporated as a component (C) into the lubricant composition of the present invention.
  • Examples of the antioxidants include an amine-based antioxidants, phenol-based antioxidants, and a sulfur-based antioxidants.
  • Examples of the amine-based antioxidants include: monoalkyldiphenylamine-based compounds such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamine-based compounds such as 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine, and 4,4′-dinonyldiphenylamine; polyalkyldiphenylamine-based compounds such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; and naphthylamine-based compounds such as α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, and nonylphenyl-α-naphthylamine. Of those, dialkyldiphenylamine-based compounds are preferable.
  • Examples of the phenol-based antioxidant include monophenol-based compounds such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol; and diphenol-based compounds such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and 2,2′-methylenebis(4-ethyl-6-tert-butylphenol).
  • Examples of the sulfur-based antioxidant include phenothiazine, pentaerythritol-tetrakis(3-laurylthiopropionate), bis(3,5-tert-butyl-4-hydroxybenzyl)sulfide, thiodiethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-methylamino)phenol.
  • Each of these antioxidants may be used alone or two or more of them may be used in combination. Further, the blending amounts of those antioxidants are typically in the range of 0.01 to 10 mass %, or preferably in a range of 0.03 to 5 mass % on the basis of the total amount of the lubricant composition.
  • As other extreme pressure agents, the wear-resisting agents, and the oiliness agents, there are exemplified organic metal compounds such as zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), oxymolybdenum organo phosphorodithioate sulfide (MODTP), and oxymolybdenum dithiocarbamate sulfide (MDTC). The blending amount of those is typically 0.05 to 5 mass %, or preferably 0.1 to 3 mass % based on the total amount of lubricant composition.
  • Further, mentioned are oiliness agents including aliphatic saturated and unsaturated monocarboxylic acids such as stearic acids and oleic acids; polymerized fatty acids such as dimer acids and hydrogenated dimer acids; hydroxy fatty acids such as ricinoleic acids and 12-hydroxystearic acids; aliphatic saturated and unsaturated monohydric alcohols such as lauryl alcohol and oleyl alcohol; aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine; and aliphatic saturated andunsaturated monocarboxylic acid amides such as lauric acid amide and oleamide.
  • The preferable blending amount of those oiliness agents is typically in a range of 0.01 to 10 mass %, or particularly preferably in a range of 0.1 to 5 mass % based on the total amount of lubricant composition.
  • Examples of the detergents and the dispersants include: ashless dispersants such as succinimides, boron-containing succinimides, benzylamines, boron-containing benzylamines, succinates, and monovalant or bivalent carboxylic amides typified by fatty acids or succinic acids; and metal-based detergents such as neutral metal sulfonate, neutral metal phenate, neutral metal salicylate, neutral metal phosphonate, basic sulfonate, basic phenate, basic salicylate, over-based sulfonate, over-based salicylate, and over-based phosphonate. The blending amount of those detergent dispersants is typically 0.1 to 20 mass %, or preferably 0.5 to 10 mass % based on the total amount of lubricant composition.
  • For example, a polymethacrylate having a weight average molecular weight of about 50,000 to 150,000 can be used as the pour point depressant.
  • An additive except those described above such as a rust inhibitor, a metal deactivator, a defoaming agent, or a surfactant can be incorporated into the lubricant composition of the present invention as desired.
  • There are used, for example: as the rust inhibitor, alkenyl succinic acid and partial esters thereof; as the metal corrosion inhibitor, benzotriazole-based, benzimidazole-based, benzothiazole-based, and thiadiazole-based ones; and as the metal deactivator, benzotriazole, benzotriazole derivatives, benzothiazole, benzothiazole derivatives, triazole, triazole derivatives, dithiocarbamate, dithiocarbamate derivatives, imidazole, and imidazole derivatives. There are used, for example: as the defoaming agent, dimethyl polysiloxane and polyacrylate; and as the surfactant, polyoxyethylene alkylphenyl ether.
  • The lubricant composition of the present invention has, for example, the following characteristics: the lubricant composition has low viscosity, is excellent in low-temperature fluidity and oxidation stability, and has a long metal fatigue life. Accordingly, the lubricant composition is suitably used as, for example, an oil for transmissions, power steering oil, shock absorber oil, or engine oil in automobiles, or a gear oil, hydraulic oil, or bearing oil for automobiles and industries; the lubricant composition is particularly suitable as an oil for transmissions such as an automatic transmission, a manual transmission, and a continuously variable transmission in automobiles.
  • EXAMPLES
  • Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but is not limited thereto.
  • It should be noted that the physical properties of a base oil and a lubricant composition were determined in accordance with the following methods.
  • <Base Oil and Lubricant Composition> (1) Kinematic Viscosity (40° C., 100° C.)
  • Measurement was performed in accordance with JIS K 2283.
  • (2) Viscosity Index (VI)
  • Measurement was performed in accordance with JIS K 2283.
  • (3) Sulfur Content
  • Measurement was performed in accordance with JIS K 2541.
  • <Base Oil> (4) Pour Point
  • Measurement was performed in accordance with JIS K 2265.
  • <Lubricant Composition> (5) Low-Temperature Viscosity (−40° C.)
  • A Brookfield viscosity at −40° C. was measured in accordance with ASTM D 2983.
  • (6) Fatigue Life
  • A fatigue life was measured with a four-ball rolling fatigue tester in the following manner.
  • (Bearing)
    Material: bearing steel
    Test piece: φ60 × 5 mm thick
    Steel ball dimensions: φ⅜ inch (⅜ × 2.54 cm)
    (Test conditions)
    Load: 147 N
    Rotational speed: 2,200 rpm
    Oil temperature: 120° C.
  • A time period required for flaking to occur in the test piece was defined as a fatigue life, and an L50 (average) was calculated from the results of the test performed six times.
  • (7) Oxidation Stability
  • A test oil was forcedly deteriorated in an ISOT test (1500° C.) in accordance with JIS K 2514. The percentage by which the viscosity changed (40° C., 100° C.), an increase in total acid number, a base number, the amount of n-heptane insoluble matter, and an increase in copper element were measured 144 hours after the deterioration.
  • The kinds of the respective components used in the preparation of a lubricant composition are as shown below.
  • Base Oils A to F
  • Table 1 shows the properties of the base oils.
  • TABLE 1
    Properties
    Kinematic Pour Sulfur
    viscosity (mm2/s) Viscosity point content
    Kind 40° C. 100° C. index (° C.) (mass %)
    Base A Hydrogenation-refined 9.79 2.686 113 −42.5 0.01>
    oil base oil
    B Hydrogenation-refined 7.976 2.252 83 −10.0 0.01>
    base oil
    C Hydrogenation-refined 20.54 4.412 127 −22.5 0.01>
    base oil
    D Hydrogenation-refined 408.8 30.86 107 −15.0 0.01>
    base oil
    E Solvent-refined 458.6 30.65 96 12.5 0.43
    base oil
    F Solvent-refined 745.8 42.52 98 15.0 0.51
    base oil
  • Ethylene/α-Olefin Copolymer I
  • A product available under the trade name “Lucant HC600” from Mitsui Chemicals, the product having a number average molecular weight of 2,600, a kinematic viscosity at 100° C. of 600 mm2/s, a viscosity index of 240, and a sulfur content of less than 0.1 mass %
  • Ethylene/α-Olefin Copolymer II
  • A product available under the trade name “Lucant HC2000” from Mitsui Chemicals, the product having a number average molecular weight of 3,700, a kinematic viscosity at 100° C. of 2,000 mm2/s, a viscosity index of 300, and a sulfur content of less than 0.1 mass % Ethylene/α-olefin copolymer III (including diluent oil having a concentration of 50 mass %)
  • A product available under the trade name “Lucant HS4010M” from Mitsui Chemicals, the product having a number average molecular weight of 6,600, a kinematic viscosity at 100° C. of 2,000 mm2/s, a viscosity index of 335, and a sulfur content of less than 0.1 mass %
  • Viscosity Index Improver I
  • A polymethacrylate-based product available under the trade name “VISCOPLEX 0-050” from Romax, the product having a number average molecular weight of 18,000 and a kinematic viscosity at 100° C. of 450 mm2/s
  • Viscosity Index Improver II
  • A polymethacrylate-based product available under the trade name “ACLUBE C728” from Sanyo Chemical Industries, Ltd., the product having a number average molecular weight of 45,000 and a kinematic viscosity at 100° C. of 852 mm2/s
  • Pour Point Depressant
  • A polymethacrylate-based product available under the trade name “ACLUBE C728” from Sanyo Chemical Industries, Ltd.
  • Extreme pressure agent: thiadiazole
  • ATF Additive Package
  • A product available under the trade name “Infineum T4261” from Infineum, the product containing a phosphorus-based extreme pressure agent, a sulfur-based extreme pressure agent, a detergent dispersant, a friction adjustor, and an antioxidant
  • Examples 1 to 4 and Comparative Examples 1 to 6
  • Lubricant compositions each having the composition shown in Table 2 were prepared, and were each evaluated for physical properties except oxidation stability. Table 2 shows the results.
  • The lubricant compositions of Example 1 and Comparative Example were each evaluated for oxidation stability. Table 3 shows the results.
  • TABLE 2
    Comparative
    Example Example
    1 2 3 4 1
    Composition Base oil Kind A A A A B/C
    (mass %) Content 84.2 84.2 83.5 84.1 35.7/44.2
    Sulfur content 0.01> 0.01> 0.01> 0.01> 0.01>
    (mass %)
    Ethylene/propylene I 2.7
    copolymer II 4.0 2.0 4.0
    III 4.0
    Viscosity index I
    improver II 8.3
    Pour point depressant 0.3 0.3 0.3 0.3 0.3
    Extreme pressure agent 0.1
    ATF additive package 11.5 11.5 11.5 11.5 11.5
    Physical Sulfur content (mass %) 0.06 0.06 0.06 0.06 0.06
    properties Kinematic viscosity  40° C. 25 26.11 26.07 24.95 33.1
    (mm2/s) 100° C. 5.64 5.806 5.775 5.63 7.37
    Viscosity index 176 176 174 176 198
    Low-temperature viscosity 7,500 7,200 9,200 7,500 14,500
    [−40° C.]
    [Brookfield viscosity]
    Fatigue life [L50] (minutes) 155 160 162 170 95
    Comparative Example
    2 3 4 5 6
    Composition Base oil Kind A/C A/C/D A/E A/F A
    (mass %) Content 19.0/66.2 50.0/25.2/ 69.2/17.0 73.5/14.0 82.4
    10.0
    Sulfur content 0.01> 0.01> 0.08 0.08 0.01>
    (mass %)
    Ethylene/propylene I 5.8
    copolymer II
    III
    Viscosity index I 2.0
    improver II 3.0 3.0 0.7
    Pour point depressant 0.3 0.3 0.3 0.3 0.3
    Extreme pressure agent
    ATF additive package 11.5 11.5 11.5 11.5 11.5
    Physical Sulfur content (mass %) 0.06 0.06 0.14 0.14 0.06
    properties Kinematic viscosity  40° C. 26.46 26.61 28.06 27.24 26.37
    (mm2/s) 100° C. 5.729 5.682 5.762 5.690 5.828
    Viscosity index 167 162 153 156 174
    Low-temperature viscosity 8,100 9,900 17,200 19,200 11,000
    [−40° C.]
    [Brookfield viscosity]
    Fatigue life [L50] (minutes) 110 135 140 155 140
  • TABLE 3
    Comparative
    Example 1 Example 5
    Oxidation Percentage by which  40° C. 3.0 8.2
    stability kinematic viscosity 100° C. 1.5 4.5
    [ISOT test changed (%)
    150° C., Increase in total acid number −0.05 0.12
    144 h] (mgKOH/g)
    Base number (mgKOH/g) 0.36 0.05
    Amount of n-pentane insoluble 0.01> 0.05
    matter (mass %)
    Increase in Cu element (ppm) 26 35
  • As can be seen from Table 2, each of the lubricant compositions of the present invention (Examples 1 to 4) has a low-temperature viscosity (−40° C.) of less than 10,000 and a fatigue life [L50] in excess of 150 minutes, so each of them has good low-temperature fluidity and a long metal fatigue life. In contrast, each of the lubricant compositions of Comparative Examples 1 to 4 and Comparative Example 6 has a fatigue life [L50] of less than 150 minutes, so each of them has a short metal fatigue life. Moreover, each of the lubricant compositions of Comparative Examples 1, 4, and 6 has a low-temperature viscosity (−40° C.) in excess of 10,000, so each of them is poor in low-temperature fluidity.
  • Meanwhile, the lubricant composition of Comparative Example 5 has a fatigue life [L50] in excess of 150 minutes, so the lubricant composition has a long metal fatigue life. However, the lubricant composition has extremely bad low-temperature fluidity. In addition, as can be seen from Table 3, the lubricant composition is inferior in oxidation stability to the lubricant composition of Example 1.
  • INDUSTRIAL APPLICABILITY
  • The lubricant composition of the present invention has the following characteristics: the lubricant composition has low viscosity, is excellent in low-temperature fluidity and oxidation stability, and has a long metal fatigue life. Accordingly, the lubricant composition is suitably used as, for example, an oil for transmissions, power steering oil, shock absorber oil, or engine oil in automobiles, or a gear oil, hydraulic oil, or bearing oil for automobiles and industries.

Claims (4)

1: A lubricant composition, comprising:
a lubricant base oil; and
0.5 to 10 mass % of (A) an ethylene/α-olefin copolymer having a number average molecular weight of 2,800 to 8,000,
wherein said lubricant base oil has a kinematic viscosity at 100° C. of 1.5 to 40 mm2/s, a viscosity index of 100 or more, a pour point of −25° C. or lower, and a sulfur content of 0.01 mass % or less.
2: The lubricant composition according to claim 1, further comprising 0.01 to 2.0 mass % of an extreme pressure agent (B) selected from the group consisting of a phosphorus-based extreme pressure agent, a sulfur-based extreme pressure agent, and a mixture thereof, the component (B) having a total sulfur content of 0.15 mass % or less.
3: The lubricant composition according to claim 2, further comprising (C) at least one kind of an additive selected from the group consisting of: an antioxidant; another extreme pressure agent; a wear-resisting agent; an oiliness agent; a detergent dispersant; and a pour point depressant.
4: A lubricant for automobile transmissions comprising the lubricant composition according to claim 1.
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CN101495607A (en) 2009-07-29
JP2008037963A (en) 2008-02-21
KR20090050051A (en) 2009-05-19
CN104277896A (en) 2015-01-14
EP2053117A1 (en) 2009-04-29
WO2008016038A1 (en) 2008-02-07
JP5350583B2 (en) 2013-11-27
EP2053117A4 (en) 2014-09-10
EP2053117B1 (en) 2020-10-28

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