WO2013136582A1 - 変速機用潤滑油組成物 - Google Patents
変速機用潤滑油組成物 Download PDFInfo
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- WO2013136582A1 WO2013136582A1 PCT/JP2012/079087 JP2012079087W WO2013136582A1 WO 2013136582 A1 WO2013136582 A1 WO 2013136582A1 JP 2012079087 W JP2012079087 W JP 2012079087W WO 2013136582 A1 WO2013136582 A1 WO 2013136582A1
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- acrylate
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- 0 CN(*)[N+]([O-])O* Chemical compound CN(*)[N+]([O-])O* 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- 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
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/011—Cloud point
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- 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
- C10N2030/02—Pour-point; Viscosity index
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- 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
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- 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
- C10N2030/08—Resistance to extreme temperature
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- 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
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
Definitions
- the present invention relates to a lubricating oil composition, and more particularly, a fuel oil saving property due to excellent viscosity-temperature characteristics, and a lubricating oil composition having excellent fatigue resistance and heat resistance despite low viscosity, particularly an automatic transmission and
- the present invention relates to a lubricating oil composition suitable for a continuously variable transmission.
- Viscosity and temperature characteristics of conventional lubricants used in automatic transmissions, manual transmissions, and internal combustion engines for improved durability and fuel efficiency such as thermal oxidation stability, wear resistance, and fatigue resistance Improvement of low temperature viscosity properties such as improvement of low temperature viscosity, improvement of low temperature fluidity, etc. are required.
- Lubricants containing various additives such as agents, friction modifiers, seal swelling agents, viscosity index improvers, antifoaming agents, and colorants are used.
- Recent transmissions and engines are required to be fuel efficient, lighter, smaller, and have higher output. Furthermore, with transmissions that are combined with higher output, improvements in power transmission capability are being pursued. . For this reason, the lubricating oil used in these products has the ability to maintain high lubrication performance while reducing product viscosity and base oil viscosity, and to prevent wear and fatigue on the surface of bearings, gears, etc., and heat resistance. Required.
- the present invention has a lubricating oil composition having excellent viscosity temperature characteristics and excellent fatigue resistance and heat resistance, and particularly suitable for an automatic transmission and / or a continuously variable transmission. It is an object of the present invention to provide a machine lubricating oil composition.
- a lubricating oil composition containing a specific additive in a specific lubricating base oil has excellent viscosity temperature characteristics and heat resistance, and has a metal fatigue life.
- the inventors have found that it can be improved and have completed the present invention.
- the present invention provides (A) a kinematic viscosity at 100 ° C. of 1.5 mm 2 / s to 3.5 mm 2 / s, a pour point of ⁇ 25 ° C. or less, a viscosity index of 110 or more, and a% CN of 2 or more. 20 or less,% C a is contained mineral base oil is 3 or less, and wherein the kinematic viscosity at 100 ° C. of the lubricating oil composition is less than 2.5 mm 2 / s or more 3.8 mm 2 / s This is a lubricating oil composition for a transmission.
- the present invention is the above-described lubricating oil composition for a transmission, wherein (A) the naphthene content of the mineral base oil is 3% by mass or more and 15% by mass or less.
- this invention contains 0.1 mass% or more and 20 mass% or less of poly (meth) acrylate containing the structural component induced
- R 1 represents hydrogen or a methyl group
- R 2 represents a hydrocarbon group having 1 to 30 carbon atoms.
- the present invention is also characterized in that the component (B) contains (B-1) poly (meth) acrylate obtained by polymerizing at least monomer components consisting of the following (Ba-1) to (Bd-1).
- the present invention is also characterized in that the component (B) contains (B-2) poly (meth) acrylate obtained by polymerizing at least monomer components consisting of the following (Ba-2) to (Bd-2).
- the (Bc-2) component is composed of the following (Bc-2-1) and (Bc-2-2): It is a thing.
- the present invention also provides the above-described transmission lubricating oil composition, wherein the composition ratio of the component (Ba-2) is 0 to 10% by mass based on the total amount of monomers.
- the (B-1) poly (meth) acrylate has a weight average molecular weight of 10,000 to 60,000 and is contained in an amount of 0.5 to 10% by mass based on the total amount of the composition.
- the present invention is the above-described lubricating oil composition for a transmission, which does not contain a pour point depressant having a weight average molecular weight of 10,000 or more and / or a viscosity index improver in addition to the component (B). .
- the lubricating oil composition of the present invention has excellent viscosity temperature characteristics and heat resistance, as well as excellent metal fatigue resistance and heat resistance. Therefore, it is particularly suitable for automatic transmissions and / or continuously variable transmissions such as automobiles, construction machines, and agricultural machines, and is also suitably used as hydraulic fluids for automobiles, construction machines, agricultural machines, machine tools, and the like.
- the component (A) in the lubricating oil composition for transmission of the present invention (hereinafter also referred to as the lubricating oil composition of the present invention) has a kinematic viscosity at 100 ° C. of 1.5 mm 2 / s to 3.5 mm 2 / s.
- the following mineral base oils The kinematic viscosity at 100 ° C. of the component (A) is preferably 2 mm 2 / s or more, more preferably 2.5 mm 2 / s or more, and further preferably 2.7 mm 2 / s or more.
- Preferably it is 3.3 mm ⁇ 2 > / s or less, More preferably, it is 3.1 mm ⁇ 2 > / s or less.
- the kinematic viscosity at 100 ° C. of the component (A) exceeds 3.5 mm 2 / s, the viscosity temperature characteristic and the low temperature viscosity characteristic deteriorate, and when it is less than 1.5 mm 2 / s, an oil film is formed at the lubrication point. Is not preferable because it is inferior in metal fatigue prevention and heat resistance, and the evaporation loss of the lubricating base oil is increased.
- the viscosity index of the mineral base oil (A) of the present invention is 110 or more, preferably 115 or more, more preferably 120 or more, and most preferably 125 or more. Further, it is preferably 160 or less, more preferably 150 or less, further preferably 140 or less, particularly preferably 135 or less, and most preferably 130 or less.
- the viscosity index is lower than 110, viscosity temperature characteristics that can exhibit fuel saving performance cannot be obtained.
- it exceeds 160 normal paraffin increases in the base oil, so that the viscosity at a low temperature increases rapidly, and the lubricity and the function as hydraulic oil are lost.
- the pour point of the component (A) is ⁇ 25 ° C. or lower, preferably ⁇ 27.5 ° C. or lower.
- the lower limit is not particularly limited, but if it is too low, it is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45 ° C. or higher, from the viewpoint of lowering the viscosity index and economical efficiency in the dewaxing process. More preferably, it is ⁇ 40 ° C. or higher, and most preferably ⁇ 37.5 ° C. or higher.
- any of solvent dewaxing and contact dewaxing steps may be applied.
- the contact dewaxing step is particularly preferable because the low temperature viscosity characteristics can be further improved.
- the% C A of Component (A) more preferably 2 or less, and more preferably 1 or less. If it exceeds 3, the heat and oxidation stability will be lowered. Although 0 may be sufficient, 0.2 or more are preferable and 0.5 or more are more preferable. This is because it is preferable for the solubilization of the additive and the extension of the fatigue life of the metal.
- the metal fatigue life can be further increased.
- the content of the saturated component (A) is not particularly limited, but is preferably 90% by mass or more, and more preferably 94% by mass in that the thermal / oxidation stability and viscosity-temperature characteristics can be further improved. More preferably, it is 98% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.
- the ratio of the cyclic saturated component to the saturated component is 3 to 15% by mass, preferably 5% by mass or more, and preferably 10% by mass or less.
- the content of the saturated component and the ratio of the cyclic saturated component in the saturated component satisfy the above conditions, viscosity-temperature characteristics and thermal / oxidative stability can be achieved.
- the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricating base oil.
- the friction characteristics of the lubricating base oil itself can be improved, and as a result, the friction reducing effect is improved. As a result, energy saving can be improved.
- the content of the saturated component is less than 90% by mass, the viscosity-temperature characteristics, thermal / oxidation stability, and friction characteristics become insufficient.
- the ratio of the cyclic saturated component to the saturated component is less than 3% by mass, when the additive is blended with the lubricating base oil, the solubility of the additive becomes insufficient, and the lubricating base oil contains Since the effective amount of the additive that is dissolved and retained is reduced, the function of the additive cannot be obtained effectively.
- the ratio of the cyclic saturated component in the saturated component exceeds 15% by mass, the effectiveness of the additive is reduced when the additive is blended with the lubricating base oil.
- the content of the saturated part as used in the field of this invention means the value (unit: mass%) measured based on ASTM D 2007-93.
- the ratio of the cyclic saturated component and the non-cyclic saturated component in the saturated component as used in the present invention refers to the cyclic saturated component measured according to ASTM D 2786-91 (measurement object: 1 to 6 ring naphthene, unit). : Mass%) and alkane content (unit: mass%).
- the aniline point of (A) component It is preferable that it is 90 degreeC or more at the point which can obtain the lubricating oil composition excellent in a low-temperature viscosity characteristic and fatigue life, More preferably, it is 95 degreeC or more, More preferably, it is 100 degreeC or more, Most preferably, it is 103 degreeC or more.
- the upper limit is not particularly limited, and may exceed 130 ° C. as one aspect of the present invention, but is preferably 130 because it is more excellent in solubility of additives and sludge and more excellent in compatibility with a sealing material. ° C or lower, more preferably 125 ° C or lower, and still more preferably 120 ° C or lower.
- the sulfur content of (A) component Preferably it is 0.1 mass% or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.01 mass% or less, Most preferably, it is substantially It is desirable not to be included.
- limiting in particular about the nitrogen content of (A) component Preferably it is 5 mass ppm or less at the point which can obtain the composition which is more excellent in thermal and oxidation stability, More preferably, it is 3 mass ppm or less, That is, it is desirable that it is not substantially contained.
- content of sulfur content and nitrogen content as used in the field of this invention means the value measured based on ASTM D4951.
- the average carbon number of the component (A) is not particularly limited, but is preferably 20 to 30, preferably 22 to 28, more preferably 23 to 27.
- the component (A) may be only one kind of mineral oil or a mixture of two or more kinds of mineral oils, but preferably one kind in order to suppress evaporability.
- the production method is not particularly limited.
- the base oils (1) to (8) shown below are used as raw materials, and the raw oils and / or the The base oil obtained by refine
- Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO) (3) Wax (such as slack wax) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-liquid (GTL) process, etc.
- WVGO Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil
- Wax such as slack wax obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-liquid (GTL) process, etc.
- the above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay purification; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning is preferable.
- hydrorefining such as hydrocracking and hydrofinishing
- solvent refining such as furfural solvent extraction
- dewaxing such as solvent dewaxing and catalytic dewaxing
- chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning is preferable.
- one of these purification methods may be performed alone, or two or more may be combined.
- the order in particular is not restrict
- the lubricating base oil according to the present invention can be obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment.
- the following base oil (9) or (10) is particularly preferred.
- the thermal / oxidative stability and low temperature viscosity characteristics can be further enhanced, and the fatigue prevention performance of the lubricating oil composition is further enhanced. It is particularly preferable to include a contact dewaxing step.
- a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary.
- catalytic dewaxing the hydrocracking / isomerization product oil is reacted with hydrogen in the presence of an appropriate dewaxing catalyst under conditions effective to lower the pour point.
- catalytic dewaxing some of the high-boiling substances in the cracking / isomerization product are converted to low-boiling substances, the low-boiling substances are separated from the heavier base oil fraction, and the base oil fraction is fractionated. Two or more kinds of lubricating base oils are obtained.
- the low-boiling substances can be separated before obtaining the target lubricating base oil or during fractional distillation.
- the dewaxing catalyst is not particularly limited as long as it can lower the pour point of the cracked / isomerized product oil, but the desired lubricating base oil is obtained from the cracked / isomerized product oil in a high yield. Those that can be used are preferred.
- a shape selective molecular sieve molecular sieve
- ferrierite, mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22 And theta aluminophosphates (SAPO) and the like.
- SAPO a aluminophosphates
- These molecular sieves are preferably used in combination with a catalytic metal component, and more preferably in combination with a noble metal.
- a preferable combination is, for example, a composite of platinum and H-mordenite.
- the dewaxing conditions are not particularly limited, but the temperature is preferably 200 to 500 ° C., and the hydrogen pressure is preferably 10 to 200 bar (1 MPa to 20 MPa). Also, in the case of flow-through reactor, H 2 processing speed is preferably 0.1 ⁇ 10kg / l / hr, LHSV is preferably 0.1 ⁇ 10h -1, more preferably 0.2 ⁇ 2.0 h -1 .
- dewaxing refers to a substance having an initial boiling point of 350 to 400 ° C., usually 40% by weight or less, preferably 30% by weight or less, contained in the cracked / isomerized product oil, having a boiling point lower than the initial boiling point. It is preferable to carry out the conversion to a substance having the same.
- various base oils can be mixed in addition to the component (A).
- base oils include mineral base oils and / or synthetic base oils.
- Mineral oil base oils include mineral oil base oils other than the component (A).
- Specific examples of synthetic base oils include polybutene or hydrides thereof; poly- ⁇ -olefins such as 1-octene oligomers, 1-decene oligomers and 1-dodecene oligomers or hydrides thereof; ditridecyl glutarate , Di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl sebacate; neopentyl glycol ester, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethyl Examples thereof include polyol esters such as hexanoate and pentaerythritol pelargonate; aromatic synthetic oils such as al
- these mineral oil base oil and / or synthetic base oil examples include one or more mineral base oils, one or more synthetic base oils, a mixed oil of one or more mineral base oils and one or more synthetic base oils, and the like.
- the content of the other base oil in the case of mixing the other base oil in the present invention needs to be 30% by mass or less based on the mixed base oil of the component (A) and the other base oil component. Preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 7 mass% or less.
- the kinematic viscosity at 100 ° C. of the mixed base oil composed of the component (A) and another base oil is the same as the case of the base oil (A) component alone. The same applies to the viscosity index.
- the transmission lubricating oil composition of the present invention preferably contains (B) poly (meth) acrylate in the base oil containing the component (A).
- the component (B) in the present invention is preferably a poly (meth) acrylate pour point depressant or / and a viscosity index improver having a structural unit represented by the following general formula (1).
- R 1 is hydrogen or a methyl group, preferably a methyl group
- R 2 is a hydrocarbon group having 1 to 30 carbon atoms.
- the component (B) in the present invention may contain a structural unit derived from a monomer represented by the following general formula (2) or general formula (3), but is not included from the viewpoint of extending the metal fatigue life. Is preferred.
- the structural unit derived from the monomer represented by the general formula (2) or the general formula (3) is included, the cleanliness is improved, and therefore there is a problem with the cleanliness of the lubricating oil composition for transmission. It is preferable to use for.
- R 3 is hydrogen or a methyl group, preferably a methyl group
- R 4 is an alkylene group having 1 to 30 carbon atoms
- E 1 is 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
- An amine residue or a heterocyclic residue to be contained is shown, and a represents an integer of 0 or 1.
- R 5 is hydrogen or a methyl group
- E 2 represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
- Specific examples of the group represented by E 1 and E 2 include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, and a benzoylamino group.
- Morpholino group pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, pyrazino group and the like.
- this include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone. And a mixture thereof.
- the production method of the poly (meth) acrylate is arbitrary, but can be easily obtained by radical solution polymerization of a mixture of monomers in the presence of a polymerization initiator such as benzoyl peroxide.
- the component (B) in the present invention may contain a structural unit having a vinyl group such as styrene in order to adjust the flexibility of the poly (meth) acrylate and the solubility with the base oil and increase the viscosity index.
- the component (B) in the present invention is specifically a copolymer obtained by polymerizing a monomer mixture in which R 2 in the general formula (1) is composed of the following monomer compositions (Ba) to (Bd): .
- R 2 is an alkyl group having 1 to 4 carbon atoms (meth) acrylate
- Bb is an alkyl group having 5 to 10 carbon atoms (meth) acrylate
- Bc is 11 to 11 carbon atoms
- R 2 which is an 18 alkyl group is a (meth) acrylate whose alkyl group has 19 or more carbon atoms
- the component (B) preferably contains (B-1) poly (meth) acrylate obtained by polymerizing the following monomer mixtures (Ba-1) to (Bd-1).
- R 2 is an alkyl group having 5 to 10 carbon atoms (meth) acrylate: a monomer total amount of from 0% or more, 30 wt% or less, preferably 20 wt% or less, more preferably 10 mass %Less than.
- (Bc-1) R 2 is an alkyl group having 11 to 18 carbon atoms (meth) acrylate: 20% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more, based on the total amount of monomers. 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less.
- R 2 is an alkyl group having 19 to 40 carbon atoms (meth) acrylate: 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly based on the total amount of monomers. Preferably it is 20 mass% or more, 50 mass% or less, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less.
- the carbon number of R 2 in the (Bd-1) component is preferably 20 or more, preferably 36 or less, more preferably 32 or less, and still more preferably 28 or less.
- the component (B) in the present invention preferably contains (B-2) poly (meth) acrylate obtained by polymerizing the following monomer mixtures (Ba-2) to (Bd-2).
- (B-2) a poly (meth) acrylate monomer in which (Ba-2) component and (Bb-2) component are each 5 mass% or less, preferably 2 mass% or less, and most preferably 0 mass%
- a preferred example is poly (meth) acrylate (B-2a) having a polymerized composition. By setting it as this composition, the low-temperature viscosity characteristic is most improved. An example of this composition was used in the examples.
- the (B-2) poly (meth) acrylate is 10% by mass or more and 40% by mass or less, does not contain the (Bb-2) component, and the (Bc-2) component is preferably
- Preferable examples include poly (meth) acrylate (B-2b) obtained by polymerizing a monomer composition of 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or less, more preferably 80% by mass or less. . By setting it as this composition, low temperature viscosity, a viscosity index, and fatigue life can be balanced. An example of this composition was used in the examples.
- (Bc-1) is composed of the following compositions (Bc-1-1) and (Bc-1-2): preferable.
- (Bc-2) is composed of the following (Bc-2-1) and (Bc-2-2) compositions among the monomers constituting (B-2). preferable.
- (Bc-2a-1) and (Bc-2b-2) were described according to (B-2a) and (B-2b), respectively.
- This composition can be particularly effective for improving the low temperature viscosity characteristics while maintaining the fatigue life improving effect.
- (B-1) has a weight average molecular weight of preferably 10,000 or more, more preferably 15,000 or more. Moreover, it is preferable that it is 60,000 or less, It is more preferable that it is 50,000 or less, It is further more preferable that it is 30,000 or less. By using this weight average molecular weight, it is particularly effective for improving shear stability and fatigue life.
- the weight average molecular weight of (B-2) is preferably 20,000 or more, and more preferably 25,000 or more. Moreover, it is preferable that it is 100,000 or less. By using this weight average molecular weight, it is effective for improving fluidity and fatigue life particularly at low temperatures.
- the weight average molecular weight of (B-2a) is preferably 40,000 or more, more preferably 50,000 or more, more preferably 80,000 or less, and even more preferably 70,000 or less.
- this weight average molecular weight in addition to improving the fatigue life, it is effective for improving fluidity particularly at low temperatures.
- the weight average molecular weight of (B-2b) is preferably 20,000 or more, more preferably 25,000 or more, and preferably 60,000 or less, preferably 40,000 or less. Is more preferable. By setting this weight average molecular weight, it is particularly effective for improving the viscosity index, shear stability and fatigue life.
- the weight average molecular weight is determined by using two columns of GHSHR-M (7.8 mm ID ⁇ 30 cm) manufactured by Tosoh Corporation in series on a 150-C ALC / GPC apparatus manufactured by Waters, and tetrahydrofuran as a solvent. It means a weight average molecular weight in terms of polystyrene measured by a temperature of 23 ° C., a flow rate of 1 mL / min, a sample concentration of 1 mass%, a sample injection amount of 75 ⁇ L, and a detector differential refractometer (RI).
- the content of the component (B) in the lubricating oil composition of the present invention is 0.1% by mass or more based on the total amount of the composition, preferably 0.2% by mass or more, more preferably 0.3% by mass or more. It is. Moreover, it is preferable that it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 6 mass% or less.
- the content of the component (B) is less than 0.1% by mass, the effect of improving the viscosity index and the effect of reducing the product viscosity are diminished, and thus there is a possibility that the fuel economy cannot be improved. Further, if it exceeds 20% by mass, it is necessary to lower the base oil viscosity. Therefore, the lubrication performance under severe lubrication conditions (high temperature and high shear conditions) is lowered, and there are problems such as wear, seizure and fatigue failure. There is a concern that it may be a cause.
- the content of the component (B-1) in the lubricating oil composition of the present invention is 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass based on the total amount of the composition. It is at least mass%. Moreover, it is preferable that it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less, Most preferably, it is 4 mass% or less.
- the content of the component (B-1) is less than 0.05% by mass, the effect of improving the viscosity index and the effect of reducing the product viscosity are diminished, so that there is a possibility that the fuel economy cannot be improved.
- the content of the component (B-2) in the lubricating oil composition of the present invention is 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass based on the total amount of the composition. It is at least mass%. Moreover, it is preferable that it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less, Most preferably, it is 4 mass% or less.
- the content is 0.05% by mass or more, preferably 0.1% by mass or more, more preferably 0.8% by mass based on the total amount of the composition. 2% by mass or more. Moreover, it is preferable that it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less, Most preferably, it is 0.5 mass% or less. If the content of (B-2a) is less than 0.05% by mass, the effect of improving the viscosity index and the effect of reducing the product viscosity are diminished, and thus there is a possibility that the fuel economy cannot be improved. Moreover, when it exceeds 3 mass%, a viscosity raise will be large and it will become disadvantageous for low temperature viscosity characteristic improvement.
- the content when the component (B-2) is (B-2b) is 0.5% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass based on the total amount of the composition. It is at least mass%. Moreover, it is preferable that it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less, Most preferably, it is 4 mass% or less. If the content of (B-2b) is less than 0.5% by mass, the effect of improving the viscosity index and the effect of reducing the product viscosity are diminished, and thus there is a possibility that the fuel economy cannot be improved. Moreover, since it will be necessary to reduce a base-oil viscosity when it exceeds 10 mass%, there exists a possibility that the lubrication performance in severe lubrication conditions (high temperature high shear conditions) may fall.
- the combination of (B-1), (B-2a) and (B-2b) in the (B) polymethacrylate component is not particularly limited as long as it matches the viscosity characteristics of the composition. However, it is preferably configured according to the added amount of each component described above. As a result, the low temperature viscosity characteristics, shear stability, viscosity index and fatigue life can be improved in the most balanced manner.
- the lubricating oil composition of the present invention comprises, in addition to the component (B), an ordinary general non-dispersed or dispersed poly (meth) acrylate, non-dispersed or dispersed ethylene- ⁇ -olefin copolymer or a copolymer thereof
- a hydride, polyisobutylene or a hydride thereof, a styrene-diene hydrogenated copolymer, a styrene-maleic anhydride ester copolymer, and a polyalkylstyrene can be further contained.
- the lubricating oil composition of the present invention preferably contains no pour point depressant or / and viscosity index improver having a weight average molecular weight of 10,000 or more in addition to the component (B). Thereby, there is no viscosity reduction due to shearing, and the lowest kinematic viscosity at 100 ° C. can be achieved, so that the fuel saving effect is maximized.
- the lubricating oil composition of the present invention can contain various additives as required as long as the excellent viscosity temperature characteristics and low temperature performance, fatigue resistance and heat resistance are not impaired.
- Such an additive is not particularly limited, and any additive conventionally used in the field of lubricating oils can be blended.
- Specific examples of such lubricant additives include metal detergents, ashless dispersants, antioxidants, extreme pressure agents, antiwear agents, friction modifiers, pour point depressants, corrosion inhibitors, and rust inhibitors. , Demulsifiers, metal deactivators, antifoaming agents and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.
- metal detergents include sulfonate detergents, salicylate detergents, phenate detergents, and the like, including any of normal salts, basic normal salts, and overbased salts with alkali metals or alkaline earth metals. Can be blended. In use, one kind or two or more kinds arbitrarily selected from these can be blended.
- any ashless dispersant used in lubricating oils can be used.
- antioxidants examples include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum.
- friction modifier examples include ashless friction modifiers such as fatty acid esters, aliphatic amines, and fatty acid amides, and metal friction modifiers such as molybdenum dithiocarbamate and molybdenum dithiophosphate.
- any extreme pressure agent and antiwear agent used in lubricating oils can be used.
- sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used.
- corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.
- rust preventive examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
- demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylene alkyl naphthyl ether.
- metal deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
- metal deactivator examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and ⁇ - (o-carboxybenzylthio) propiononitrile.
- antifoaming agents examples include silicone oils having a kinematic viscosity at 25 ° C. of less than 0.1 to 100 mm 2 / s, alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, methyl salicylates and o -Hydroxybenzyl alcohol and the like.
- the content is preferably 0.1 to 20% by mass based on the total amount of the composition.
- the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is not particularly limited, but is preferably 3.8 mm 2 / s or less, more preferably 3.7 mm 2 / s or less, and even more preferably 3 .6mm 2 / s or less, and most preferably not more than 3.5 mm 2 / s. Moreover, it is preferably 2.5 mm 2 / s or more, more preferably 2.6 mm 2 / s or more, further preferably 2.7 mm 2 / s or more, and particularly preferably 3 mm 2 / s or more.
- the viscosity index of the lubricating oil composition of the present invention is not particularly limited, but is preferably 120 or more, more preferably 140 or more, and still more preferably 160 or more from the viewpoint of fuel economy.
- the Brookfield (BF) viscosity at ⁇ 40 ° C. of the lubricating oil composition of the present invention is preferably 15000 mPa ⁇ s or less, more preferably 10,000 mPa ⁇ s or less, still more preferably 8000 mPa ⁇ s or less, and even more preferably 5000 mPa ⁇ s. ⁇ S or less, particularly preferably 3000 mPa ⁇ s or less, most preferably 2500 mPa ⁇ s or less.
- the Brookfield viscosity referred to here is a value measured by ASTM D2983.
- the lubricating oil composition of the present invention is a lubricating oil composition having excellent wear resistance and fatigue resistance and excellent low-temperature fluidity, and is particularly suitable as an automatic transmission oil and / or continuously variable transmission oil. It is.
- the lubricating oil composition of the present invention is also excellent in performance as a transmission oil other than the above, and is used for automatic transmissions such as automobiles, construction machines, and agricultural machines, manual transmissions, and differential gears. Also preferably used.
- lubricating oils that require wear resistance, fatigue resistance, and low temperature viscosity characteristics such as industrial gear oils, automobiles such as motorcycles and automobiles, power generation, marine gasoline engines, diesel engines, gas, etc. It can also be suitably used for engine lubricating oil, turbine oil, compressor oil, and the like.
- Examples 1 to 6 and Comparative Examples 1 and 2 As shown in Table 1, lubricating oil compositions of the present invention (Examples 1 to 6) and comparative lubricating oil compositions (Comparative Examples 1 and 2) were prepared. The obtained composition was measured for kinematic viscosity, low-temperature viscosity characteristics, fatigue resistance, four-ball wear resistance, and oxidation stability. The results are also shown in Table 1.
- Base oil A-1 mineral oil [100 ° C. kinematic viscosity: 2.84 mm 2 / s, 40 ° C. kinematic viscosity: 10.4 mm 2 / s, viscosity index: 125, aniline point: 114 ° C.,% C P : 92,% C A : 0,% C N : 7.8, pour point: -30.0 ° C, S content: 1 mass ppm or less, N content: 3 mass ppm or less, naphthene content is 5 mass%] [2] Base oil A-2: mineral oil [100 ° C.
- kinematic viscosity 2.74 mm 2 / s, 40 ° C.
- kinematic viscosity 10.2 mm 2 / s, viscosity index: 109, aniline point: 104 ° C.,% C P : 75,% C A : 1,% C N : 23.5, pour point: -27.5 ° C, S content: 1 mass ppm or less, N content: 3 mass ppm or less, naphthene content is 5 mass%]
- Base oil A-3 mineral oil [100 ° C. kinematic viscosity: 2.08 mm 2 / s, 40 ° C.
- R 2 is an alkyl group having 5 to 10 carbon atoms: content 0 mass% (Bc-2b-1)
- R 2 is an alkyl group having 11 to 15 carbon atoms: 76% by mass
- R 2 is an alkyl group having 16 to 18 carbon atoms: content 0 mass%
- R 2 is an alkyl group having 19 or more carbon atoms: 0% by mass
- ⁇ Other additives C-1> 1.5% by mass of nitrogen, 1.5% by mass of boron, succinimide having an alkenyl group molecular weight of 2000: 3% by mass, Thiadiazole with 7% by mass of nitrogen: 0.2% by mass Amine antioxidant that is 4% by mass of nitrogen: 0.5% by mass Metal-based detergent that is 10% by weight of calcium: 0.1% by weight Succinimide friction modifier that is 6% by mass of nitrogen: 1.0% by mass Ester friction modifier: 0.5% by mass Ester seal swelling agent: 0.3% by mass
- Thrust needle bearing surface pressure: 1.9 GPa, rotation speed: 1410 rpm, oil temperature: 120 ° C.
- LNSL maximum non-seizure load
- Comparative Example 1 which does not use the component (A) as the lubricating base oil is inferior in viscosity temperature characteristics, low temperature viscosity characteristics and fatigue resistance.
- Comparative Example 2 in which the component (A) is not used is also inferior in fatigue resistance and heat resistance and has low temperature viscosity characteristics.
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Description
しかしながら、上記手法だけでは粘度温度特性および低温性能と疲労防止性、耐熱性の両立が十分に図れておらず、これらの性能を両立させつつその他の諸性能についても問題ない性能を有する潤滑油組成物の開発が求められている。
(Ba-1)R2が炭素数1~4のアルキル基である(メタ)アクリレート:20~60質量%
(Bb-1)R2が炭素数5~10のアルキル基である(メタ)アクリレート:0~30質量%
(Bc-1)R2が炭素数11~18のアルキル基である(メタ)アクリレート:20~70質量%
(Bd-1)R2が炭素数19~40のアルキル基である(メタ)アクリレート:5~50質量%
(Ba-2)R2が炭素数1~4のアルキル基である(メタ)アクリレート:0~60質量%
(Bb-2)R2が炭素数5~10のアルキル基である(メタ)アクリレート:0~30質量%
(Bc-2)R2が炭素数11~18のアルキル基である(メタ)アクリレート:30~100質量%
(Bd-2)R2が炭素数19以上のアルキル基である(メタ)アクリレート:0質量%
(Bc-2-1)R2が炭素数11~15のアルキル基である(メタ)アクリレート:60~100質量%((Bc-2)基準)。
(Bc-2-2)R2が炭素数16~18のアルキル基である(メタ)アクリレート:0~40質量%((Bc-2)基準)。
(A)成分の100℃における動粘度は、好ましく2mm2/s以上であり、より好ましくは2.5mm2/s以上、さらに好ましくは2.7mm2/s以上である。また、好ましくは3.3mm2/s以下であり、より好ましくは3.1mm2/s以下である。
(A)成分の100℃における動粘度が3.5mm2/sを超える場合は、粘度温度特性及び低温粘度特性が悪化し、1.5mm2/s未満の場合は、潤滑箇所での油膜形成が不十分であるため金属疲労防止性、耐熱性に劣り、また潤滑油基油の蒸発損失が大きくなるため、それぞれ好ましくない。
なお、脱ろう工程としては溶剤脱ろう、接触脱ろうのいずれの工程を適用してもよいが、低温粘度特性をより改善できる点で接触脱ろう工程であることが特に好ましい。
また、本発明でいう飽和分に占める環状飽和分及び非環状飽和分の割合とは、それぞれASTM D 2786-91に準拠して測定される環状飽和分(測定対象:1~6環ナフテン、単位:質量%)及びアルカン分(単位:質量%)を意味する。
(A)成分の窒素分については特に制限はないが、より熱・酸化安定性に優れる組成物を得ることができる点で、好ましくは5質量ppm以下であり、より好ましくは3質量ppm以下、すなわち実質的に含まれないことが望ましい。
なお、本発明でいう硫黄分及び窒素分の含有量とは、ASTM D4951に準拠して測定される値を意味する。
(1)パラフィン基系原油及び/又は混合基系原油の常圧蒸留による留出油
(2)パラフィン基系原油及び/又は混合基系原油の常圧蒸留残渣油の減圧蒸留による留出油(WVGO)
(3)潤滑油脱ろう工程により得られるワックス(スラックワックス等)及び/又はガストゥリキッド(GTL)プロセス等により得られる合成ワックス(フィッシャートロプシュワックス、GTLワックス等)
(4)基油(1)~(3)から選ばれる1種又は2種以上の混合油及び/又は当該混合油のマイルドハイドロクラッキング処理油
(5)基油(1)~(4)から選ばれる2種以上の混合油
(6)基油(1)、(2)、(3)、(4)又は(5)の脱れき油
(7)基油(6)のハイドロクラッキング処理油
(8)基油(1)~(7)から選ばれる2種以上の混合油
(10)上記基油(1)~(8)から選ばれる基油又は当該基油から回収された潤滑油留分を水素化異性化し、その生成物又はその生成物から蒸留等により回収される潤滑油留分について溶剤脱ろうや接触脱ろうなどの脱ろう処理を行い、または、当該脱ろう処理をしたあとに蒸留することによって得られる水素化異性化鉱油
また、上記(9)又は(10)の潤滑油基油を得るに際して、必要に応じて溶剤精製処理及び/又は水素化仕上げ処理工程を更に設けてもよい。
鉱油系基油としては、(A)成分以外の鉱油系基油が挙げられる。また合成系基油としては、具体的には、ポリブテン又はその水素化物;1-オクテンオリゴマー、1-デセンオリゴマー、1-ドデセンオリゴマー等のポリ-α-オレフィン又はその水素化物;ジトリデシルグルタレート、ジ-2-エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、及びジ-2-エチルヘキシルセバケート等のジエステル;ネオペンチルグリコールエステル、トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール-2-エチルヘキサノエート、及びペンタエリスリトールペラルゴネート等のポリオールエステル;アルキルナフタレン、アルキルベンゼン、及び芳香族エステル等の芳香族系合成油又はこれらの混合物等が例示できる。
本発明における他の基油を混合する場合の他の基油の含有量は、(A)成分と他の基油成分の混合基油を基準として、30質量%以下であることが必要であり、好ましくは20質量%以下であり、より好ましくは10質量%以下、更に好ましくは7質量%以下である。
本発明における(B)成分としては、下記一般式(1)で表される構造単位を有するポリ(メタ)アクリレート系流動点降下剤または/および粘度指数向上剤が好ましい。
なお一般式(2)や一般式(3)で表されるモノマーから誘導される構成単位を含む場合は、清浄性が向上するため、変速機用潤滑油組成物の清浄性に問題がある場合に使用することが好ましい。
(Ba)R2が炭素数1~4のアルキル基である(メタ)アクリレート
(Bb)R2が炭素数5~10のアルキル基である(メタ)アクリレート
(Bc)R2が炭素数11~18のアルキル基である(メタ)アクリレート
(Bd)R2が炭素数19以上のアルキル基である(メタ)アクリレート
(Ba-1)R2が炭素数1~4のアルキル基である(メタ)アクリレート:モノマー全量基準で、20質量%以上、好ましくは25質量%以上、より好ましくは30質量%以上、更に好ましくは33質量%以上で、60質量%以下、好ましくは50質量%以下、より好ましくは45質量%以下、さらに好ましくは40質量%以下。
(Bb-1)R2が炭素数5~10のアルキル基である(メタ)アクリレート:モノマー全量基準で、0質量%以上、30質量%以下、好ましくは20質量%以下、より好ましくは10質量%以下。
(Bc-1)R2が炭素数11~18のアルキル基である(メタ)アクリレート:モノマー全量基準で、20質量%以上、より好ましくは30質量%以上、更に好ましくは35質量%以上で、70質量%以下、好ましくは60質量%以下、より好ましくは50質量%以下。
(Bd-1)R2が炭素数19~40のアルキル基である(メタ)アクリレート:モノマー全量基準で、5質量%以上、より好ましくは10質量%以上、更に好ましくは15質量%以上、特に好ましくは20質量%以上で、50質量%以下、好ましくは40質量%以下、より好ましくは30質量%以下。
なお(Bd-1)成分のR2の炭素数は20以上が好ましく、好ましくは36以下、より好ましくは32以下、さらに好ましくは28以下である。
(Bb-2)R2が炭素数5~10のアルキル基である(メタ)アクリレート:モノマー全量基準で、0質量%以上、30質量%以下、好ましくは20質量%以下、より好ましくは10質量%以下、最も好ましくは0質量%。
(Bc-2)R2が炭素数11~18のアルキル基である(メタ)アクリレート:モノマー全量基準で、30質量%以上、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは80質量%以上、特に好ましくは90質量%以上で、100質量%以下、好ましくは95質量%以下。
(Bd-2)R2が炭素数19以上のアルキル基である(メタ)アクリレート:0質量%。
(Bc-1-1)R2が炭素数11~15のアルキル基である(メタ)アクリレート:60質量%以上、好ましくは65質量%以上、より好ましくは70質量%以上、更に好ましくは85質量%以上で、100質量%以下。
(Bc-1-2)R2が炭素数16~18のアルキル基である(メタ)アクリレート:0質量%以上40質量%以下。
(Bc-2-1)R2が炭素数11~15のアルキル基である(メタ)アクリレート:60質量%以上、好ましくは65質量%以上、より好ましくは70質量%以上、更に好ましくは85質量%以上で、100質量%以下。
(Bc-2-2)R2が炭素数16~18のアルキル基である(メタ)アクリレート:0質量%以上40質量%以下。
なお、実施例には、(B-2a)および(B-2b)に準じて、それぞれ(Bc-2a-1)および(Bc-2b-2)と記載した。
(B)成分の含有量が0.1質量%より少なくなると、粘度指数向上効果や製品粘度の低減効果が小さくなることから、省燃費性の向上が図れなくなるおそれがある。また、20質量%よりも多くなると、基油粘度を低下させる必要が出てくることから、厳しい潤滑条件(高温高せん断条件)における潤滑性能を低下させ、摩耗や焼き付き、疲労破壊等の不具合が発生原因となることが懸念される。
(B-1)成分の含有量が0.05質量%より少なくなると、粘度指数向上効果や製品粘度の低減効果が小さくなることから、省燃費性の向上が図れなくなるおそれがある。また、10質量%よりも多くなると、基油粘度を低下させる必要が出てくることから、厳しい潤滑条件(高温高せん断条件)における潤滑性能を低下させ、摩耗や焼き付き、疲労破壊等の不具合が発生原因となることが懸念される。
(B-2a)の含有量が0.05質量%より少なくなると、粘度指数向上効果や製品粘度の低減効果が小さくなることから、省燃費性の向上が図れなくなるおそれがある。また、3質量%よりも多くなると粘度上昇が大きく、低温粘度特性改善に不利になる。
(B-2b)の含有量が0.5質量%より少なくなると、粘度指数向上効果や製品粘度の低減効果が小さくなることから、省燃費性の向上が図れなくなるおそれがある。また、10質量%よりも多くなると、基油粘度を低下させる必要が出てくることから、厳しい潤滑条件(高温高せん断条件)における潤滑性能を低下が懸念される。
ここで言うブルックフィールド粘度とは、ASTM D2983により測定される値である。
また、本発明の潤滑油組成物は、上記以外の変速機油としての性能にも優れており、自動車、建設機械、農業機械等の自動変速機用あるいは手動変速機用、ディファレンシャルギヤ用の潤滑油としても好適に用いられる。その他、摩耗防止性、疲労防止性及び低温粘度特性が要求される潤滑油、例えば、工業用ギヤ油、二輪車、四輪車等の自動車用、発電用、舶用等のガソリンエンジン、ディーゼルエンジン、ガスエンジン用の潤滑油、タービン油、圧縮機油等にも好適に使用することができる。
表1に示すように、本発明の潤滑油組成物(実施例1~6)、比較用の潤滑油組成物(比較例1~2)をそれぞれ調製した。得られた組成物について、動粘度、低温粘度特性、疲労防止性、四球耐摩耗性、さらに酸化安定性を測定し、その結果を同じく表1に併記した。
<基油>
[1]基油A-1:鉱油[100℃動粘度:2.84mm2/s、40℃動粘度:10.4mm2/s、粘度指数:125、アニリン点:114℃、%CP:92、%CA:0、%CN:7.8、流動点:-30.0℃、S量:1質量ppm以下、N量:3質量ppm以下、ナフテン分が5質量%]
[2]基油A-2:鉱油[100℃動粘度:2.74mm2/s、40℃動粘度:10.2mm2/s、粘度指数:109、アニリン点:104℃、%CP:75、%CA:1、%CN:23.5、流動点:-27.5℃、S量:1質量ppm以下、N量:3質量ppm以下、ナフテン分が5質量%]
[3]基油A-3:鉱油[100℃動粘度:2.08mm2/s、40℃動粘度:6.87mm2/s、粘度指数:96、アニリン点:89℃、%CP:63、%CA:6、%CN:32.4、流動点:-25.0℃、S量:800質量ppm、N量:20質量ppm]
[1](B-1):モノマー組成が以下の(Ba-1)~(Bd-1)からなり、重量平均分子量が20000であるポリメタクリレート
(Ba-1)R2が炭素数1のアルキル基:含有割合34質量%
(Bb-1)R2が炭素数5~10のアルキル基:含有割合質量0%
(Bc-1-1)R2が炭素数11~15のアルキル基:含有割合6質量%
(Bc-1-2)R2が炭素数16~18のアルキル基:含有割合34質量%
(Bd-1)R2が炭素数19以上のアルキル基:含有割合24質量%
[2](B-2a):モノマー組成が以下の(Ba-2a)~(Bd-2a)からなり、重量平均分子量が61000であるポリメタクリレート
(Ba-2a)R2が炭素数1のアルキル基:含有割合2質量%
(Bb-2a)R2が炭素数5~10のアルキル基:含有割合0質量%
(Bc-2a-1)R2が炭素数11~15のアルキル基:含有割合90質量%
(Bc-2a-2)R2が炭素数16~18のアルキル基:含有割合8質量%
(Bd-2a)R2が炭素数19以上のアルキル基:含有割合0質量%
[3](B-2b):モノマー組成が以下の(Ba-2b)~(Bd-2b)からなり、重量平均分子量が30000であるポリメタクリレート
(Ba-2b)R2が炭素数1のアルキル基:含有割合24質量%
(Bb-2b)R2が炭素数5~10のアルキル基:含有割合0質量%
(Bc-2b-1)R2が炭素数11~15のアルキル基:含有割合76質量%
(Bc-2b-2)R2が炭素数16~18のアルキル基:含有割合0質量%
(Bd-2b)R2が炭素数19以上のアルキル基:含有割合0質量%
窒素1.5質量%、ホウ素1.5質量%、アルケニル基分子量2000であるコハク酸イミド:3質量%、
窒素7質量%であるチアジアゾール:0.2質量%
窒素4質量%であるアミン系酸化防止剤:0.5質量%
カルシウム10質量%である金属系清浄剤:0.1質量%
窒素6質量%であるコハク酸イミド系摩擦調整剤:1.0質量%
エステル系摩擦調整剤:0.5質量%
エステル系シール膨潤剤:0.3質量%
ASTM D2983に準拠し、各潤滑油組成物の-40℃におけるBF粘度を測定した。本試験においては、BF粘度の値が小さいものほど低温流動性に優れていることを意味する。
(2)疲労防止性
高温転がり疲労試験機を用いて、以下の試験条件でピッチング発生寿命を評価した。また、比較例1の試験結果を基準として、ピッチング発生寿命の比を算出した。本試験においては、疲労寿命比(L50比およびL10比)が大きいほど疲労防止性能に優れていることを意味する。
スラストニードルベアリング(面圧:1.9GPa、回転数:1410rpm、油温:120℃)
(3)高速四球耐熱性
ASTM D2596に準拠し、高速四球試験機を用い、各潤滑油組成物の1800回転における最大非焼付き荷重(LNSL)を測定した。本試験においては、最大非焼付き荷重が大きいほど耐熱性に優れていることを意味する。
(4)酸化安定性
JIS K2514 4.(内燃機関用潤滑油酸化安定度試験方法)に準拠して実施し、酸価増加およびペンタン不溶分を測定した。
一方、潤滑油基油として(A)成分を使用しない比較例1は、粘度温度特性、低温粘度特性及び疲労防止性に劣る。同様に(A)成分を使用しない比較例2も、疲労防止性や耐熱性に劣り、低温粘度特性も不十分である。
Claims (9)
- (A)100℃における動粘度が1.5mm2/s以上3.5mm2/s以下、流動点が-25℃以下、粘度指数が110以上、%CNが2以上20以下、%CAが3以下である鉱油系基油を含有し、潤滑油組成物の100℃における動粘度が2.5mm2/s以上3.8mm2/s以下であることを特徴とする変速機用潤滑油組成物。
- (A)鉱油系基油のナフテン分が3質量%以上15質量%以下であることを特徴とする請求項1に記載の変速機用潤滑油組成物。
- (B)成分が、少なくとも下記(Ba-1)~(Bd-1)からなるモノマー成分を重合して得られる(B-1)ポリ(メタ)アクリレートを含むことを特徴とする請求項3に記載の変速機用潤滑油組成物。
(Ba-1)R2が炭素数1~4のアルキル基である(メタ)アクリレート:20~60質量%
(Bb-1)R2が炭素数5~10のアルキル基である(メタ)アクリレート:0~30質量%
(Bc-1)R2が炭素数11~18のアルキル基である(メタ)アクリレート:20~70質量%
(Bd-1)R2が炭素数19~40のアルキル基である(メタ)アクリレート:5~50質量% - (B)成分が、少なくとも下記(Ba-2)~(Bd-2)からなるモノマー成分を重合して得られる(B-2)ポリ(メタ)アクリレートを含むことを特徴とする請求項3に記載の変速機用潤滑油組成物。
(Ba-2)R2が炭素数1~4のアルキル基である(メタ)アクリレート:0~60質量%
(Bb-2)R2が炭素数5~10のアルキル基である(メタ)アクリレート:0~30質量%
(Bc-2)R2が炭素数11~18のアルキル基である(メタ)アクリレート:30~100質量%
(Bd-2)R2が炭素数19以上のアルキル基である(メタ)アクリレート:0質量% - 前記(Bc-2)成分が、下記(Bc-2-1)と(Bc-2-2)から構成されていることを特徴とする請求項5に記載の変速機用潤滑油組成物。
(Bc-2-1)R2が炭素数11~15のアルキル基である(メタ)アクリレート:60~100質量%((Bc-2)基準)。
(Bc-2-2)R2が炭素数16~18のアルキル基である(メタ)アクリレート:0~40質量%((Bc-2)基準)。 - 前記(Ba-2)成分の組成割合が、モノマー全量基準で0~10質量%であることを特徴とする請求項5または請求項6に記載の変速機用潤滑油組成物。
- (B-1)ポリ(メタ)アクリレートの重量平均分子量が10,000~60,000であり、組成物全量基準で0.5~10質量%含有し、(B-2)ポリ(メタ)アクリレートの重量平均分子量が20,000~100,000であり、組成物全量基準で0.05~10質量%含有することを特徴とする請求項5~請求項7のいずれかに記載の変速機用潤滑油組成物。
- (B)成分以外に重量平均分子量1万以上の流動点降下剤または/および粘度指数向上剤を含有しないことを特徴とする請求項1~請求項8のいずかに記載の変速機用潤滑油組成物。
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| CN112166175B (zh) * | 2018-06-08 | 2023-10-27 | 出光兴产株式会社 | 润滑油组合物和浸渍轴承 |
| CN112166175A (zh) * | 2018-06-08 | 2021-01-01 | 出光兴产株式会社 | 润滑油组合物和浸渍轴承 |
| US11560527B2 (en) | 2019-02-20 | 2023-01-24 | Eneos Corporation | Lubricating oil composition for transmission |
| WO2020171188A1 (ja) * | 2019-02-20 | 2020-08-27 | Jxtgエネルギー株式会社 | 変速機用潤滑油組成物 |
| JP7482851B2 (ja) | 2019-02-20 | 2024-05-14 | Eneos株式会社 | 変速機用潤滑油組成物 |
| JPWO2020171188A1 (ja) * | 2019-02-20 | 2021-12-23 | Eneos株式会社 | 変速機用潤滑油組成物 |
| US11214755B2 (en) | 2019-04-10 | 2022-01-04 | Eneos Corporation | Lubricating oil composition |
| DE102020002249B4 (de) | 2019-04-10 | 2022-03-24 | Jxtg Nippon Oil & Energy Corporation | Schmierölzusammensetzung und deren Verwendung |
| JP7324732B2 (ja) | 2019-04-10 | 2023-08-10 | Eneos株式会社 | 潤滑油組成物 |
| JP2020172642A (ja) * | 2019-04-10 | 2020-10-22 | Eneos株式会社 | 潤滑油組成物 |
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| WO2020213644A1 (ja) * | 2019-04-16 | 2020-10-22 | Jxtgエネルギー株式会社 | 変速機用潤滑油組成物 |
| WO2024058119A1 (ja) | 2022-09-16 | 2024-03-21 | Eneos株式会社 | 潤滑油組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| US9340747B2 (en) | 2016-05-17 |
| CN104160002B (zh) | 2016-03-30 |
| JPWO2013136582A1 (ja) | 2015-08-03 |
| JP5841657B2 (ja) | 2016-01-13 |
| EP2826840A1 (en) | 2015-01-21 |
| US20150057202A1 (en) | 2015-02-26 |
| EP2826840B1 (en) | 2021-06-30 |
| EP2826840A4 (en) | 2015-12-30 |
| CN104160002A (zh) | 2014-11-19 |
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