WO2014017556A1 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- WO2014017556A1 WO2014017556A1 PCT/JP2013/070092 JP2013070092W WO2014017556A1 WO 2014017556 A1 WO2014017556 A1 WO 2014017556A1 JP 2013070092 W JP2013070092 W JP 2013070092W WO 2014017556 A1 WO2014017556 A1 WO 2014017556A1
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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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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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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- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- 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
- C10M2215/28—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
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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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
- C10N2030/54—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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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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
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
Definitions
- the present invention relates to a lubricating oil composition.
- lubricating oil is used in internal combustion engines, transmissions, and other mechanical devices in order to make their operations smooth.
- lubricating oil (engine oil) for internal combustion engines is required to have high performance as the performance of the internal combustion engine increases, the output increases, and the operating conditions become severe. Therefore, various additives such as antiwear agents, metal detergents, ashless dispersants, and antioxidants are blended in conventional engine oils in order to satisfy these required performances (for example, Patent Documents 1 to 5 listed below). 3).
- Patent Documents 1 to 5 listed below listed below. 3
- HTHS viscosity is also called “high temperature high shear viscosity”
- it is effective to lower the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C., but it has been very difficult to satisfy all these requirements with conventional lubricating oils.
- the present invention has been made in view of such circumstances, and the kinematic viscosity at 40 ° C. and the kinematic viscosity at 100 ° C. can be lowered over a long period from the initial stage to after use, and the viscosity after shearing.
- An object of the present invention is to provide a lubricating oil composition excellent in durability and fuel-saving properties capable of suppressing the decrease.
- the present invention provides a lubricating base oil having a kinematic viscosity at 100 ° C. of 1 to 10 mm 2 / s, and (A) one type of structural unit represented by the following general formula (1) Or a lubricating oil composition comprising a branched poly (meth) acrylate viscosity index improver having a ratio of two or more of 30 to 90 mol% and a degree of branching of 0.1 to 8.0. Offer things.
- R 1 represents hydrogen or a methyl group
- R 2 represents a linear or branched hydrocarbon group having 6 or less carbon atoms.
- the (A) viscosity index improver is preferably a viscosity index improver having a PSSI of 5 or less and a ratio of molecular weight to PSSI (Mw / PSSI) of 2 ⁇ 10 4 or more.
- the lubricating oil composition preferably further contains (B) a friction modifier.
- PSSI as used in the present invention conforms to ASTM D 6022-01 (Standard Practicing for Calculation of Permanent Shear Stable Property Index), and is ASTM D 6278-02 (Test MetalstoSheetMoldShortSordfordP Means the permanent shear stability index of a polymer, calculated based on data measured by European Diesel Injector Apparatus.
- the kinematic viscosity at 40 ° C. and the kinematic viscosity at 100 ° C. can be sufficiently lowered over a long period from the beginning to after use. It is possible to provide a lubricating oil composition that can sufficiently suppress a decrease in viscosity after shearing and is excellent in durability and fuel saving.
- the lubricating oil composition of the present invention can also be suitably used for gasoline engines, diesel engines, gas engines, etc. for motorcycles, automobiles, power generation, cogeneration, etc. Not only can it be suitably used for these various engines using fuel of ppm or less, but it is also useful for various engines for ships and outboard motors.
- the lubricating oil composition according to this embodiment comprises a lubricating base oil having a kinematic viscosity at 100 ° C. of 1 to 10 mm 2 / s and (A) one of structural units represented by the following general formula (1): A branched poly (meth) acrylate viscosity index improver having a ratio of two or more of 30 to 90 mol% and a degree of branching of 0.1 to 8.0 is contained. [In the formula (1), R 1 represents hydrogen or a methyl group, and R 2 represents a linear or branched hydrocarbon group having 6 or less carbon atoms. ]
- a lubricating base oil (hereinafter referred to as “the lubricating base oil according to the present embodiment”) having a kinematic viscosity at 100 ° C. of 1 to 10 mm 2 / s is used. .
- a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, Paraffinic mineral oil, or normal paraffinic base oil, isoparaffinic base oil, etc., refined by combining one or more of refining treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc.
- refining treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc.
- those having a kinematic viscosity at 100 ° C. of 1 to 5 mm 2 / s can be mentioned.
- the following base oils (1) to (8) are used as raw materials, and the raw oil and / or the lubricating oil fraction recovered from the raw oil is The base oil obtained by refine
- recovering lubricating oil fractions can be mentioned.
- 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 (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-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 refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred.
- 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 embodiment is 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 base oil selected from the above base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like.
- Hydrocracking base oil (10) obtained by subjecting the lubricating oil fraction to dewaxing treatment such as solvent dewaxing or catalytic dewaxing, or distillation after the dewaxing treatment, and the above base oils (1) to (The base oil selected from 8) or the lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic desorption. Hydroisomerized base oil obtained by performing dewaxing treatment such as wax or by distillation after the dewaxing treatment.
- a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.
- the catalyst used for the hydrocracking / hydroisomerization is not particularly limited, but a composite oxide having cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one kind of the composite oxide.
- Hydrogenolysis with a combination of the above combined with a binder and supporting a metal having hydrogenation ability for example, one or more metals such as Group VIa metal or Group VIII metal in the periodic table
- a hydroisomerization catalyst in which a catalyst or a support containing zeolite (eg, ZSM-5, zeolite beta, SAPO-11, etc.) is loaded with a metal having a hydrogenation ability containing at least one of the Group VIII metals are preferably used.
- the hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.
- reaction conditions for hydrocracking and hydroisomerization are not particularly limited, but hydrogen partial pressure 0.1 to 20 MPa, average reaction temperature 150 to 450 ° C., LHSV 0.1 to 3.0 hr-1, hydrogen / oil ratio 50 to 20000 scf / b is preferable.
- the kinematic viscosity at 100 ° C. of the lubricating base oil according to this embodiment needs to be 10 mm 2 / s or less, preferably 4.5 mm 2 / s or less, more preferably 4 mm 2 / s or less, preferably 3.8 mm 2 / s or less, particularly preferably 3.7 mm 2 / s or less, and most preferably not more than 3.6 mm 2 / s.
- the kinematic viscosity at 100 ° C. needs to be 1 mm 2 / s or more, preferably 1.5 mm 2 / s or more, more preferably 2 mm 2 / s or more, and still more preferably 2.
- the kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
- the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 10 mm 2 / s, the worse the low temperature viscosity characteristics, also there is a risk that can not be obtained sufficient fuel saving properties, the following cases 1 mm 2 / s Since the formation of an oil film at the lubrication site is insufficient, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.
- the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present embodiment is preferably 40 mm 2 / s or less, more preferably 30 mm 2 / s or less, still more preferably 25 mm 2 / s or less, and particularly preferably 20 mm 2. / S or less, and most preferably 17 mm 2 / s or less.
- kinematic viscosity at 40 ° C. is preferably 6.0 mm 2 / s or more, more preferably 8.0 mm 2 / s or more, further preferably 10 mm 2 / s or more, particularly preferably 12 mm 2 / s or more, most preferably Preferably it is 14 mm ⁇ 2 > / s or more.
- the lubricating base oil exceeds 40 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, less 6.0 mm 2 / s In such a case, the oil film formation at the lubrication site is insufficient, so that the lubricity is poor, and the evaporation loss of the lubricating oil composition may be increased.
- the viscosity index of the lubricating base oil according to this embodiment is preferably 100 or more. More preferably, it is 105 or more, More preferably, it is 110 or more, Especially preferably, it is 115 or more, Most preferably, it is 120 or more.
- the viscosity index is less than 100, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. .
- the viscosity index as used in the present invention means a viscosity index measured according to JIS K 2283-1993.
- the lubricating base oil used in the lubricating oil composition according to the present embodiment has a first lubricating base oil component having a kinematic viscosity at 100 ° C. of 3.5 mm 2 / s or more and a viscosity index of 120 or more, and 100 A mixture of the second lubricating base oil component having a kinematic viscosity at less than 3.5 mm 2 / s is preferred.
- a mixture of the first lubricating base oil component and the second lubricating base oil component it is possible to impart excellent viscosity temperature characteristics and further improve fuel economy.
- the density ( ⁇ 15 ) at 15 ° C. of the first lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 0.860 or less, more preferably 0.850 or less, and still more preferably 0.00. It is 840 or less, particularly preferably 0.822 or less.
- the density at 15 ° C. in the present invention means a density measured at 15 ° C. in accordance with JIS K 2249-1995.
- the pour point of the first lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 12.5 ° C. or lower, even more preferably ⁇ 15 ° C. or lower, especially Preferably, it is ⁇ 20 ° C. or lower.
- the pour point as used in the present invention means a pour point measured according to JIS K 2269-1987.
- the kinematic viscosity at 100 ° C. of the first lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 5 mm 2 / s or less, more preferably 4.5 mm 2 / s or less, and further Preferably it is 4.0 mm ⁇ 2 > / s or less, Most preferably, it is 3.9 mm ⁇ 2 > / s or less.
- the kinematic viscosity at 100 ° C. is preferably 3.5 mm 2 / s or more, more preferably 3.6 mm 2 / s or more, still more preferably 3.7 mm 2 / s or more, and particularly preferably 3. 8 mm 2 / s or more.
- the kinematic viscosity at 100 ° C. is more than 5 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 3.5 mm 2 / s at lubricating sites Insufficient oil film formation may result in poor lubricity and increase in evaporation loss of the lubricating oil composition.
- the kinematic viscosity at 40 ° C. of the first lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 40 mm 2 / s or less, more preferably 30 mm 2 / s or less, and even more preferably 25 mm 2 / s. s or less, particularly preferably 20 mm 2 / s or less, and most preferably 17 mm 2 / s or less.
- kinematic viscosity at 40 ° C. is more than 40 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel saving properties, the following cases 6.0 mm 2 / s at lubricating sites Insufficient oil film formation may result in poor lubricity and increase in evaporation loss of the lubricating oil composition.
- the viscosity index of the first lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 100 or more. More preferably, it is 110 or more, More preferably, it is 120 or more, Especially preferably, it is 130 or more, Most preferably, it is 140 or more. Further, it is preferably 170 or less, more preferably 160 or less, further preferably 155 or less, and particularly preferably 150 or less.
- the viscosity index is less than 100, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. .
- the viscosity index exceeds 170, the low-temperature viscosity increases, and the fuel efficiency at low oil temperature tends to deteriorate, and the startability tends to deteriorate.
- the density ( ⁇ 15 ) at 15 ° C. of the second lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 0.860 or less, more preferably 0.850 or less, and even more preferably 0.8. It is 840 or less, particularly preferably 0.835 or less.
- the pour point of the second lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 12.5 ° C. or lower, even more preferably ⁇ 15 ° C. or lower, particularly Preferably, it is ⁇ 20 ° C. or lower.
- the pour point exceeds the upper limit, the low temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease.
- the kinematic viscosity at 100 ° C. of the second lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably less than 3.5 mm 2 / s, more preferably 3.4 mm 2 / s or less. More preferably, it is 3.3 mm 2 / s or less.
- the kinematic viscosity at the 100 ° C. is preferably 2 mm 2 / s or more, more preferably 2.5 mm 2 / s or more, further preferably 3.0 mm 2 / s or more.
- the kinematic viscosity at 40 ° C. of the second lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 20 mm 2 / s or less, more preferably 18 mm 2 / s or less, and even more preferably 16 mm 2 / s. s or less, particularly preferably 14 mm 2 / s or less.
- kinematic viscosity at 40 ° C. is more than 20 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel saving properties, the following cases 6.0 mm 2 / s at lubricating sites Insufficient oil film formation may result in poor lubricity and increase in evaporation loss of the lubricating oil composition.
- the viscosity index of the second lubricating base oil component used in the lubricating oil composition according to this embodiment is preferably 100 or more. More preferably, it is 105 or more, More preferably, it is 110 or more. Further, it is preferably 160 or less, more preferably 150 or less, further preferably 140 or less, and particularly preferably 135 or less.
- the viscosity index is less than 100, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. .
- the viscosity index exceeds 160, the low-temperature viscosity increases, and the fuel economy at low oil temperature tends to deteriorate, and the startability tends to deteriorate.
- the sulfur content in the lubricating base oil used in this embodiment depends on the sulfur content of the raw material.
- a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
- a lubricating base oil that does not substantially contain sulfur can be obtained.
- the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it.
- the content of sulfur is preferably 100 ppm by mass or less, and 50 ppm by mass or less, from the viewpoint of further improvement in thermal and oxidation stability and low sulfur content. More preferably, it is more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.
- the nitrogen content in the lubricating base oil used in the present embodiment is preferably 7 mass ppm or less, more preferably 5 mass ppm or less, and even more preferably 3 mass ppm or less. If the nitrogen content exceeds 5 ppm by mass, the thermal and oxidation stability tends to decrease.
- the nitrogen content in the present invention means a nitrogen content measured according to JIS K 2609-1990.
- The% C p of the lubricating base oil used in the present embodiment is preferably 70 or more, preferably 80 or more, more preferably 85 or more, still more preferably 87 or more, and particularly preferably 90 or more. . Further, it is preferably 99.9 or less, more preferably 98 or less, still more preferably 96 or less, and particularly preferably 94 or less.
- % C p of lubricating base oil is less than the above lower limit, viscosity-temperature characteristics, thermal / oxidative stability, and friction characteristics tend to decrease, and when additives are added to lubricating base oil In addition, the effectiveness of the additive tends to decrease. Further, when the% C p value of the lubricating base oil exceeds the upper limit value, the additive solubility will tend to be lower.
- % C A of the lubricating base oil used in the present embodiment is preferably 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less.
- % C A of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.
- % C N of the lubricating base oil used in the present embodiment is preferably 30 or less, preferably 25 or less, more preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less . Further, it is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and particularly preferably 6 or more. If the% C N value of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties will tend to be reduced. Moreover, when% CN is less than the said lower limit, it exists in the tendency for the solubility of an additive to fall.
- % C P in the present invention % C A N and% C A, obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number
- the preferred ranges of% C P ,% C N and% C A described above are based on the values obtained by the above method. For example, even for a lubricating base oil containing no naphthene, it can be obtained by the above method.
- is% C N may indicate a value greater than zero.
- the content of the saturated component in the lubricating base oil used in the present embodiment is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass based on the total amount of the lubricating oil base oil.
- the ratio of the cyclic saturated component in the saturated component is preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, more preferably 25%. It is at most 21% by mass, more preferably at most 21% by mass.
- annular saturated part which occupies for the said saturated part becomes like this. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more.
- the viscosity-temperature characteristics and the heat / oxidation stability can be improved.
- 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. Furthermore, according to the present embodiment, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in friction reduction effect and an improvement in energy saving.
- the saturated part as used in the field of this invention is measured by the method described in said ASTM D 2007-93.
- a similar method that can obtain the same result can be used for the separation method of the saturated component or the composition analysis of the cyclic saturated component and the non-cyclic saturated component.
- a method described in ASTM D 2425-93, a method described in ASTM D 2549-91, a method using high performance liquid chromatography (HPLC), a method obtained by improving these methods, and the like can be given.
- the aromatic content in the lubricating base oil used in the present embodiment is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 2% by mass or less, based on the total amount of the lubricating oil base oil. Especially preferably, it is 1 mass% or less, Preferably it is 0.1 mass% or more, More preferably, it is 0.2 mass% or more. If the aromatic content exceeds the above upper limit, the viscosity-temperature characteristics, thermal / oxidative stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to decrease. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present embodiment may not contain an aromatic component, but the solubility of the additive is further increased by setting the aromatic content to be equal to or higher than the above lower limit value. be able to.
- the aromatic content in the present invention means a value measured according to ASTM D 2007-93.
- the aromatic component includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols and naphthols. Aromatic compounds having atoms are included.
- a synthetic base oil may be used as the lubricating base oil according to the present embodiment.
- Synthetic base oils include poly ⁇ -olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate) having a kinematic viscosity at 100 ° C. of 1 to 10 mm 2 / s.
- the production method of poly- ⁇ -olefin is not particularly limited.
- Friedel Crafts containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester examples thereof include a method of polymerizing ⁇ -olefin in the presence of a polymerization catalyst such as a catalyst.
- the lubricating base oil according to the present embodiment may be used alone, and the lubricating base oil according to the present embodiment may be one of other base oils or You may use together with 2 or more types.
- the ratio of the lubricating base oil which concerns on this embodiment in those mixed base oils is 30 mass% or more Is more preferable, it is more preferable that it is 50 mass% or more, and it is still more preferable that it is 70 mass% or more.
- a kinematic viscosity at 100 ° C. is 10 mm 2 / s, greater 1000 mm 2 / s or less Solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil, solvent dewaxing base oil, and the like.
- Other synthetic base oils used in combination with the lubricating base oil according to this embodiment include the above-described synthetic base oils having a kinematic viscosity at 100 ° C. outside the range of 1 to 10 mm 2 / s. It is done.
- (A) the proportion of one or more structural units represented by the following general formula (1) is 30 to 90 mol%, and the degree of branching is 0. 1 to 8.0 of a branched poly (meth) acrylate viscosity index improver (hereinafter referred to as “viscosity index improver according to the present embodiment” for convenience).
- viscosity index improver a branched poly (meth) acrylate viscosity index improver
- the branched poly (meth) acrylate viscosity index improver having a proportion of structural units represented by the following general formula (1) of 30 to 90 mol% and a degree of branching of 0.1 to 8.0.
- the form of the compound is arbitrary.
- Specific examples of the compound include non-dispersed or dispersed poly (meth) acrylate viscosity index improvers, (meth) acrylate-olefin copolymers, and mixtures thereof.
- R 1 represents hydrogen or a methyl group
- R 2 represents a linear or branched hydrocarbon group having 6 or less carbon atoms.
- R 2 in the structural unit represented by the formula (1) is a linear or branched hydrocarbon group having 6 or less carbon atoms as described above, and may be one kind or a mixture of two or more kinds. Preferably, it is a linear or branched hydrocarbon having 4 or less carbon atoms, more preferably a linear or branched hydrocarbon having 3 or less carbon atoms, more preferably a carbon having 2 or less carbon atoms. It is a hydrogen group.
- the proportion of the (meth) acrylate structural unit represented by the general formula (1) in the polymer is 30 to 90 mol% as described above, but preferably 85 The mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less, and particularly preferably 70 mol% or less. Moreover, it is 30 mol% or more preferably, More preferably, it is 35 mol% or more, More preferably, it is 40 mol% or more.
- the solubility in base oil and the effect of improving viscosity temperature characteristics and low temperature viscosity characteristics may be inferior, and if it is less than 30 mol%, the effect of improving viscosity temperature characteristics may be inferior.
- (A) the proportion of one or more structural units represented by the following general formula (2) is preferably 0.1 to 50 mol%.
- R 3 represents hydrogen or a methyl group
- R 4 represents a linear or branched hydrocarbon group having 16 or more carbon atoms.
- R 4 in the structural unit represented by the formula (2) is preferably one or a mixture of two or more linear or branched hydrocarbon groups having 16 or more carbon atoms.
- a linear or branched hydrocarbon group having 17 or more carbon atoms is more preferable, and a linear or branched hydrocarbon group having 18 or more carbon atoms is more preferable.
- the proportion of the (meth) acrylate structural unit represented by the general formula (2) in the polymer is preferably 0.1 to 50 mol% as described above. More preferably, it is 45 mol% or less, More preferably, it is 40 mol% or less, Especially preferably, it is 35 mol% or less, Most preferably, it is 30 mol% or less. Further, it is preferably 0.2 mol% or more, more preferably 1 mol% or more, further preferably 5 mol% or more, particularly preferably 10 mol% or more, and most preferably 20 mol% or more. .
- the effect of improving viscosity temperature characteristics may be inferior, and if it is less than 0.1 mol%, it may be inferior in solubility in base oil, low-temperature viscosity characteristics, or even the effect of improving viscosity temperature characteristics. There is.
- the viscosity index improver according to this embodiment may be a copolymer having an arbitrary (meth) acrylate structural unit in addition to the (meth) acrylate structural unit represented by the general formulas (1) and (2). .
- Such a copolymer is represented by one or more monomers represented by the following general formula (3) (hereinafter referred to as “monomer (M-1)”) and the following general formula (4). Obtained by copolymerizing one or more monomers (hereinafter referred to as “monomer (M-2)”) with a monomer other than the monomer (M-1) and the monomer (M-2). Can do.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a linear or branched hydrocarbon group having 6 or less carbon atoms.
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents a linear or branched hydrocarbon group having 16 or more carbon atoms.
- Monomers to be combined with the monomer (M-1) and the monomer (M-2) are arbitrary, but for example, a monomer represented by the following general formula (5) (hereinafter referred to as “monomer (M-3)”) is preferable. It is.
- the monomer (M-1) and the copolymer of the monomer (M-2) and the monomer (M-3) are so-called non-dispersed poly (meth) acrylate viscosity index improvers.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a linear or branched hydrocarbon group having 7 to 15 carbon atoms.
- R 6 in the structural unit represented by the formula (5) is a linear or branched hydrocarbon group having 7 to 15 carbon atoms, preferably a linear or branched group having 10 or more carbon atoms. More preferably, it is a linear or branched hydrocarbon having 11 or more carbon atoms, and more preferably a branched hydrocarbon group having 12 or more carbon atoms.
- the (meth) acrylate structural unit represented by the general formula (5) in the polymer may be one type or a mixture of two or more types, but the ratio is 60 mol% or less, more preferably 50 mol% or less, still more preferably 45 mol% or less, particularly preferably 40 mol% or less, and most preferably 30 mol% or less. . If it exceeds 60 mol%, the effect of improving viscosity temperature characteristics and low temperature viscosity characteristics may be inferior, and if it is less than 0.5 mol%, the effect of improving viscosity temperature characteristics may be inferior.
- a monomer represented by the following general formula (6) hereinafter referred to as “monomer (M-4)”
- monomer (M-5) One or more selected from monomers represented by formula (7)
- the copolymer of the monomer (M-1), (M-2) and the monomer (M-4) and / or (M-5) is a so-called dispersed poly (meth) acrylate viscosity index improver.
- the dispersion type poly (meth) acrylate viscosity index improver may further contain a monomer (M-3) as a constituent monomer.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents an alkylene group having 1 to 18 carbon atoms
- E 1 represents 1 to 2 nitrogen atoms and 0 to 0 oxygen atoms
- 2 represents an amine residue or a heterocyclic residue
- a represents 0 or 1.
- alkylene group having 1 to 18 carbon atoms represented by R 6 include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, Examples include an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group (these alkylene groups may be linear or branched).
- Specific examples of the group represented by E 1 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, a benzoylamino group, Examples thereof include morpholino group, pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, and pyrazino group.
- R 7 represents a hydrogen atom or a hydrocarbon group
- E 2 represents an amine residue or a heterocyclic ring containing 1 to 2 hydrocarbon groups or nitrogen atoms and 0 to 2 oxygen atoms. Indicates residue.
- Specific examples of the group represented by 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, a benzoylamino group, and a morpholino group.
- Preferable examples of the monomers (M-4) and (M-5) include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, Examples thereof include morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone and a mixture thereof.
- the method for producing the viscosity index improver according to the present embodiment is not particularly limited.
- an alkyl methacrylate that forms an arm part (polymer chain of alkyl methacrylate) is polymerized, and then, Examples include a method of reacting a polyalkyl methacrylate with a polyfunctional compound having two or more ethylenically unsaturated double bonds.
- Controlled radical polymerization processes include atom transfer radical polymerization (ATRP) processes, reversible addition-fragmentation chain transfer (RAFT) processes, or nitrogen oxide mediated polymerization processes.
- ATRP atom transfer radical polymerization
- RAFT reversible addition-fragmentation chain transfer
- nitrogen oxide mediated polymerization processes A discussion of the polymer mechanism of ATRP polymerization is given by Matyjaszewski et al., Reaction Scheme 11.1 on page 524, Reaction Scheme 11.1 on page 564, Reaction Scheme 11.4 on page 571, Reaction Scheme 11 on page 571, Reaction Schemes 11.8 and 575 on page 572. The reaction scheme on page 11.9 is shown.
- a discussion of the polymer mechanism of RAFT polymerization is given in Matjajaszewski et al., Section 12.4.4, pages 664-665.
- the above synthesis can be performed as a batch operation, semi-batch operation, continuous process, feed process or bulk process.
- the synthesis can also be made in an emulsion, solution or suspension.
- the average molecular weight of the resulting polymethacrylate or viscosity index improver is adjusted by changing the amount of initiator and polyfunctional compound having two or more ethylenically unsaturated double bonds. can do.
- the reaction rate to the viscosity index improver using the synthesized arm portion is 70% or more, preferably 80% or more, more preferably 85% or more, based on the amount of the polymer reacted with the viscosity index improver. is there. If the reaction rate is low, the arm portion remains and the molecular weight cannot be increased.
- the PSSI (Permanent Cystability Index) in the diesel injector method of the viscosity index improver according to this embodiment is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, particularly preferably 5 or less, and most preferably 3 It is as follows. When PSSI exceeds 20, the shear stability is poor, and the kinematic viscosity and HTHS viscosity after use are kept at a certain level or more, so that the initial fuel economy may be deteriorated.
- the “PSSI in the Diesel Injector Method” here is based on ASTM D 6022-01 (Standard Practication for Calculation of Permanent Shear Stability Index). Means the permanent shear stability index of the polymer, calculated based on the data measured by USING a European Diesel Injector Apparatus.
- the weight average molecular weight (M w ) of the viscosity index improver is preferably 100,000 or more, more preferably 200,000 or more, still more preferably 300,000 or more, particularly Preferably it is 400,000 or more. Moreover, it is preferable that it is 1,000,000 or less, More preferably, it is 900,000 or less, More preferably, it is 700,000 or less, Especially preferably, it is 600,000 or less.
- the weight average molecular weight is less than 100,000, the effect of improving the viscosity index when dissolved in a lubricating base oil is small, and the fuel economy and low temperature viscosity characteristics are inferior, and the cost may increase.
- M W / PSSI PSSI ratio of the weight average molecular weight and diesel injectors method of viscosity index improver according to the present embodiment
- M W / PSSI is preferably 1.0 ⁇ 10 4 or more, more preferably 2.0 ⁇ 10 4 or more, more preferably 5.0 ⁇ 10 4 or more, and particularly preferably 8.0 ⁇ 10 4 or more. If M W / PSSI is below 1.0 ⁇ 10 4, there is a possibility that fuel saving properties and low-temperature startability i.e. viscosity temperature characteristics and low temperature viscosity characteristics are deteriorated.
- the ratio (M W / M N ) between the weight average molecular weight (M W ) and the number average molecular weight (M N ) of the viscosity index improver according to this embodiment is preferably 5.0 or less, more preferably 4. It is 0 or less, more preferably 3.5 or less, particularly preferably 3.0 or less, and most preferably 2.0 or less. Further, it is preferred that the M W / M N is 1.0 or more, more preferably 1.1 or more, more preferably 1.2 or more. When M W / M N is 4.0 or more or 1.0 or less, there is a possibility that sufficient storage stability and fuel economy cannot be maintained due to deterioration of solubility and viscosity temperature characteristics. .
- the degree of branching of the viscosity index improver according to this embodiment is 0.1 to 8.0, more preferably 6.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, particularly Preferably it is 2.5 or less, Most preferably, it is 2.0 or less. Moreover, Preferably it is 0.2 or more, More preferably, it is 0.5 or more, More preferably, it is 1.0 or more.
- the degree of branching exceeds 8.0, the viscosity temperature characteristic and the fuel efficiency are deteriorated.
- the degree of branching is less than 0.1, the viscosity-temperature characteristics and fuel economy are deteriorated, and the shear stability and durability may be deteriorated.
- the “branch degree” as used in the present invention is the ratio of the number of carbon atoms derived from the monomer constituting the main chain which is the longest atomic chain in the molecule and the number of carbon atoms derived from the monomer constituting the arm branched therefrom. (Number of carbon atoms in the arm portion / number of carbon atoms constituting the main chain).
- the number of carbon atoms derived from the monomer constituting the main chain refers to the number of carbon atoms in the two longest arm parts, and constitutes a branched arm part
- the number of carbon atoms derived from the monomer to be used refers to the number of carbon atoms in the other arm portion.
- the degree of branching is a value calculated based on the number of carbon atoms in the arm part, and does not include the number of carbon atoms in the core part.
- the following formula schematically shows an example of a star polymer.
- This star-shaped polymer has six arm parts connected to the core part, and the carbon number of the longest arm part is A, and the carbon number of the second longest arm part is B.
- the degree of branching in this case is (C + D + E + F) / (A + B).
- the content of the viscosity index improver according to this embodiment is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, based on the total amount of the composition. Particularly preferred is 5 to 20% by mass.
- the content of the viscosity index improver is less than 0.1% by mass, the effect of improving the viscosity index and the effect of reducing the product viscosity are reduced, and thus there is a possibility that the fuel economy cannot be improved.
- it exceeds 50% by mass the product cost will increase significantly and the viscosity of the base oil will need to be reduced. Therefore, the lubrication performance under severe lubrication conditions (high temperature and high shear conditions) will be reduced and wear will be reduced. There is a concern that defects such as burn-in, seizure and fatigue failure may be the cause.
- the lubricating oil composition according to the present embodiment is not only the viscosity index improver according to the present embodiment described above, but also a normal general non-dispersion type or dispersion type poly (meth) acrylate, non-dispersion type or dispersion type.
- the content of the viscosity index improver in the lubricating oil composition according to this embodiment is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, based on the total amount of the composition.
- the amount is preferably 1.0 to 15% by mass, more preferably 1.5 to 12% by mass. If the content is less than 0.1% by mass, the low temperature characteristics may be insufficient, and if the content exceeds 50% by mass, the shear stability of the composition may be deteriorated.
- the lubricating oil composition according to the present embodiment preferably contains (B) a friction modifier.
- B a friction modifier
- As a friction modifier 1 or more types of friction modifiers chosen from an organic molybdenum compound and an ashless friction modifier are mentioned.
- organic molybdenum compound used in the present embodiment examples include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, and orthomolybdic acid.
- sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC)
- molybdenum compounds for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide
- orthomolybdic acid examples include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxid
- Molybdate such as paramolybdic acid, (poly) sulfurized molybdate, metal salts of these molybdates, molybdate such as ammonium salt, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polysulfide molybdenum , Sulfurized molybdic acid, metal salts or amine salts of sulfurized molybdic acid, molybdenum halides such as molybdenum chloride, etc.) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mercaptothia Azoles, thiocarbonates, tetrahydrocarbyl thiuram disulfides, bis (di (thio) hydrocarbyl dithiophosphonates) disulfides, organic (poly) sulfides, sulf
- organic molybdenum compound an organic molybdenum compound that does not contain sulfur as a constituent element can be used.
- organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.
- the lubricating oil composition when an organic molybdenum compound is used, its content is not particularly limited, but based on the total amount of the lubricating oil composition, preferably in terms of molybdenum element, preferably 0.001% by mass or more, More preferably 0.005% by mass or more, further preferably 0.01% by mass or more, particularly preferably 0.03% by mass or more, and preferably 0.2% by mass or less, more preferably 0.1% by mass. % Or less, more preferably 0.08 mass% or less, and particularly preferably 0.06 mass% or less.
- the content When the content is less than 0.001% by mass, the friction reduction effect due to the addition tends to be insufficient, and the fuel economy and thermal / oxidation stability of the lubricating oil composition tend to be insufficient. . On the other hand, when the content exceeds 0.2% by mass, an effect commensurate with the content cannot be obtained, and the storage stability of the lubricating oil composition tends to decrease.
- any compound usually used as a friction modifier for lubricating oil can be used.
- one or two selected from oxygen atom, nitrogen atom, sulfur atom in the molecule examples thereof include compounds having 6 to 50 carbon atoms and containing at least a hetero element. More specifically, it has at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a straight chain alkyl group, straight chain alkenyl group, branched alkyl group or branched alkenyl group having 6 to 30 carbon atoms in the molecule.
- Ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, fatty alcohols, aliphatic ethers, urea compounds, hydrazide compounds, and the like.
- the content of the ashless friction modifier in the lubricating oil composition according to this embodiment is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably, based on the total amount of the lubricating oil composition. Is 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
- the content of the ashless friction modifier is less than 0.01% by mass, the effect of reducing friction due to the addition tends to be insufficient, and when the content exceeds 3% by mass, the effect of an antiwear additive or the like. Tends to be inhibited, or the solubility of the additive tends to deteriorate.
- the (B) friction modifier is preferably an organic molybdenum friction modifier, more preferably an organic molybdenum compound containing sulfur, and even more preferably molybdenum dithiocarbamate.
- the lubricating oil composition according to this embodiment may contain any additive generally used in lubricating oils depending on the purpose in order to further improve its performance.
- additives include metal detergents, ashless dispersants, antiwear agents (or extreme pressure agents), antioxidants, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, Examples thereof include additives such as an antifoaming agent.
- the content thereof is preferably 0.01 to 10% by mass based on the total amount of the lubricating oil composition.
- the kinematic viscosity at 100 ° C. of the lubricating oil composition according to this embodiment is preferably 4 to 12 mm 2 / s, preferably 9.0 mm 2 / s or less, more preferably 8.0 mm 2 / s or less, More preferably, it is 7.0 mm ⁇ 2 > / s or less, Most preferably, it is 6.8 mm ⁇ 2 > / s or less.
- the kinematic viscosity at 100 ° C. of the lubricating oil composition according to the present embodiment is preferably 4.5 mm 2 / s or more, more preferably 5.0 mm 2 / s or more, and further preferably 5.5 mm 2 / s or more.
- the kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the kinematic viscosity at 100 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and if it exceeds 12 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
- the kinematic viscosity at 40 ° C. of the lubricating oil composition according to this embodiment is preferably 4 to 50 mm 2 / s, preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less, particularly preferably 30 mm. 2 / s or less, most preferably 28 mm 2 / s or less.
- the kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present embodiment is preferably 15 mm 2 / s or more, more preferably 18 mm 2 / s or more, further preferably 20 mm 2 / s or more, and particularly preferably 22 mm 2.
- the kinematic viscosity at 40 ° C. here refers to the kinematic viscosity at 40 ° C. as defined in ASTM D-445. If the kinematic viscosity at 40 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and if it exceeds 50 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
- the viscosity index of the lubricating oil composition according to this embodiment is preferably in the range of 140 to 400, preferably 180 or more, more preferably 190 or more, still more preferably 200 or more, particularly preferably 210 or more, and most preferably. Is 215 or more.
- the viscosity index of the lubricating oil composition according to this embodiment is less than 140, it may be difficult to improve fuel economy while maintaining the HTHS viscosity of 150 ° C., and further at ⁇ 35 ° C. It may be difficult to reduce the low temperature viscosity.
- the viscosity index of the lubricating oil composition according to the present embodiment is 400 or more, there is a possibility that the evaporability may be deteriorated, and further, a problem due to insufficient solubility of the additive and compatibility with the sealing material. May occur.
- the HTHS viscosity at 100 ° C. of the lubricating oil composition according to this embodiment is preferably 5.5 mPa ⁇ s or less, more preferably 5.0 mPa ⁇ s or less, even more preferably 4.7 mPa ⁇ s or less, particularly Preferably it is 4.5 mPa * s or less, Most preferably, it is 4.4 mPa * s or less. Further, it is preferably 3.0 mPa ⁇ s or more, more preferably 3.5 mPa ⁇ s or more, particularly preferably 4.0 mPa ⁇ s or more, and most preferably 4.1 mPa ⁇ s or more.
- the HTHS viscosity at 100 ° C. referred to in the present embodiment refers to the high temperature and high shear viscosity at 100 ° C. defined in ASTM D4683.
- the HTHS viscosity at 100 ° C. is less than 3.0 mPa ⁇ s, there is a risk of insufficient lubricity, and when it exceeds 5.5 mPa ⁇ s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.
- the HTHS viscosity at 150 ° C. of the lubricating oil composition according to the present embodiment is preferably less than 4.0 mPa ⁇ s, more preferably 2.7 mPa ⁇ s or less, further preferably 2.5 mPa ⁇ s or less, Particularly preferably, it is 2.4 mPa ⁇ s or less. Further, it is preferably 2.0 mPa ⁇ s or more, more preferably 2.1 mPa ⁇ s or more, further preferably 2.2 mPa ⁇ s or more, and particularly preferably 2.3 mPa ⁇ s or more.
- HTHS viscosity at 150 ° C. is less than 2.0 mPa ⁇ s, the lubricity may be insufficient, and if it exceeds 4.0 mPa ⁇ s, sufficient fuel saving performance may not be obtained.
- the ratio of the HTHS viscosity at 150 ° C. to the HTHS viscosity at 100 ° C. (HTHS viscosity at 150 ° C./HTHS viscosity at 100 ° C.) of the lubricating oil composition according to the present embodiment is preferably 0.50 or more. More preferably, it is 0.52 or more, More preferably, it is 0.53, Most preferably, it is 0.54 or more. If the ratio is less than 0.50, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained.
- the lubricating oil composition according to the present embodiment sufficiently reduces the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C. in an engine oil having an HTHS viscosity at 150 ° C. of less than 2.6 mPa ⁇ s.
- the increase in the friction coefficient in the boundary lubrication region can be sufficiently suppressed, and the fuel efficiency is excellent.
- the lubricating oil composition according to this embodiment having such excellent characteristics can be suitably used as a fuel-saving engine oil such as a fuel-saving gasoline engine oil and a fuel-saving diesel engine oil.
- the obtained arm molecule had a weight average molecular weight of 87400, a number average molecular weight (Mn) of 62000, and a dispersity (Mw / Mn) of 1.41.
- ⁇ Synthesis of star polymer> After adding 0.07 parts by mass of azobisisobutyronitrile (AIBN) and 2.14 parts by mass of ethylene glycol dimethacrylate to the above arm solution, polymerization reaction was carried out at a solution temperature of 80 ° C. for 12 hours in a nitrogen atmosphere.
- AIBN azobisisobutyronitrile
- non-dispersed PMA viscosity index improver A-1 a target star-shaped polymer (hereinafter referred to as “non-dispersed PMA viscosity index improver A-1”) solution was obtained.
- the obtained non-dispersed PMA viscosity index improver A-1 has a weight average molecular weight (Mw) of 570,000, a number average molecular weight (Mn) of 470,000, and a dispersion degree ( Mw / Mn) was 1.23, PSSI was 3.8, and Mw / PSSI was 1.5 ⁇ 10 5 .
- the non-dispersed PMA viscosity index improver A-1 had an arm conversion of 64% by mass, an average number of arms of 8, and a degree of branching of 3.0.
- the arm conversion rate and the average number of arms are values calculated based on the following equations, respectively.
- the weight average molecular weight and number average molecular weight were determined by using three TSKgel Super MultiPore HZ-M columns (4.6 mm ID ⁇ 15 cm) manufactured by Tosoh Corporation in series with an HLC-8220 GPC apparatus manufactured by Tosoh Corporation. Tetrahydrofuran was used as the solvent.
- Synthesis Example 2 Synthesis of non-dispersed PMA viscosity index improver A-2) Instead of the arm molecule solution of Synthesis Example 1, 70 mol% of methyl methacrylate and 30 mol% of the methacrylate molecule in which R4 in the general formula (4) is an alkyl group having 18 carbon atoms (weight average molecular weight 54000, number average molecular weight) (Mn) 42000, dispersity (Mw / Mn) 1.29) except that an arm molecule solution was used, and a star-shaped polymer (hereinafter referred to as “non-dispersed PMA system”) in the same manner as in Synthesis Example 1. Viscosity index improver A-2 ”) was synthesized.
- the obtained non-dispersed PMA viscosity index improver A-2 has Mw of 490,000, Mn of 410,000, Mw / Mn of 1.19, PSSI of 2.2, and Mw / PSSI of 2.2 ⁇ 10 5.
- the degree of branching was 3.9.
- Synthesis Example 3 Synthesis of non-dispersed PMA viscosity index improver A-3) Instead of the arm molecule solution of Synthesis Example 1, 70 mol% of methyl methacrylate and 30 mol% of the methacrylate molecule in which R4 in the general formula (4) is an alkyl group having 18 carbon atoms (weight average molecular weight 85000, number average molecular weight) (Mn) 60000, dispersity (Mw / Mn) 1.42) Except that an arm molecule solution was used, a star-shaped polymer (hereinafter referred to as “non-dispersed PMA system” was used in the same manner as in Synthesis Example 1. Viscosity index improver A-3 ”) was synthesized.
- the obtained non-dispersed PMA viscosity index improver A-3 had Mw of 450,000, Mn of 380,000, Mw / Mn of 1.19, PSSI of 3.0, and Mw / PSSI of 1.5 ⁇ 10 5.
- the degree of branching was 2.0.
- Example 1 Comparative Examples 1 to 4
- lubricating oil compositions having the compositions shown in Table 2 were prepared using the following base oils and additives, respectively.
- Table 1 shows the properties of the base oils O-1, O-2, and O-3.
- A-2 Non-dispersed PMA viscosity index improver (70 mol% methyl methacrylate, 30 mol% methacrylate in which R 2 in the general formula (3) is an alkyl group having 18 carbon atoms, a small amount of polymerization Copoly
- the lubricating oil compositions of Examples 1 to 4 containing the component (A) have a low kinematic viscosity and a HTHS viscosity at 100 ° C., and a small decrease in viscosity after the ultrasonic shear test.
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Abstract
Description
更に省燃費性を向上しつつ、耐久性を維持するためには新油時の動粘度や100℃におけるHTHS粘度を低減しつつ、使用による粘度低下を低減することが重要である。また、可能な限り動粘度を低減しつつ、境界潤滑領域の摩擦係数を低減することも重要となる。
(1)パラフィン基系原油および/また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および/また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)および/また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種または2種以上の混合油および/また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)または(5)の脱れき油(DAO)
(7)基油(6)のマイルドハイドロクラッキング処理油(MHC)
(8)基油(1)~(7)から選ばれる2種以上の混合油。
(9)上記基油(1)~(8)から選ばれる基油または当該基油から回収された潤滑油留分を水素化分解し、その生成物また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後に蒸留することによって得られる水素化分解基油
(10)上記基油(1)~(8)から選ばれる基油また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、その生成物また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基油。
ATRP重合の重合体機構の論述は、Matyjaszewskiらの524ページの反応スキーム11.1、566ページの反応スキーム11.4、571ページの反応スキーム11、7、572ページの反応スキーム11.8および575ページの反応スキーム11.9で示されている。
RAFT重合の重合体機構の論述は、Matyjaszewskiらの12.4.4節の664~665ページで示されている。
窒素酸化物媒介重合(10章、463~522ページ)、ATRP(11章、523~628ページ)およびRAFT(12章、629~690ページ)の詳細な説明は、「Handbookof Radical Polymerization」(Krzysztof Matyjaszewski and Thomas P.Davis著、著作権2002、JohnWiley and Sons Inc.により出版(以下、「Matyjaszewskiら」と呼ぶ)で示されている。
<アーム(腕)分子の合成>
錨型金属製攪拌翼(真空シール付)、ジムロート冷却器、窒素導入用3方コック、およびサンプル導入口を装着した300ml 5口セパラブルフラスコに、メチルメタクリレート25.2質量部、一般式(3)中のR4が炭素数18のアルキル基であるメタクリレート36.5質量部、溶媒として炭化水素系溶剤(SAE10)120質量部を投入し、攪拌下に均一溶液とした。本溶液を氷浴にて0℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気/窒素パージを5回実施した。さらに窒素フロー下にサンプル導入口よりラジカル開始剤としてアゾビスイソブチロニトリル(AIBN)を0.27質量部、1,4-シクロヘキサジエン0.013質量部およびヨウ素0.11質量部を投入した後、窒素雰囲気下にて溶液温度80℃にて12時間重合を実施し、アーム分子溶液を得た。
GPC分析(標準物質:ポリスチレン)の結果、得られたアーム分子の重量平均分子量は87400、数平均分子量(Mn)は62000、分散度(Mw/Mn)は1.41であった。
<星型高分子の合成>
上記アーム溶液にアゾビスイソブチロニトリル(AIBN)0.07質量部、およびエチレングリコールジメタクリレート2.14質量部を添加した後、窒素雰囲気下で溶液温度80℃にて12時間重合反を実施し、目的とする星形高分子(以下、「非分散型PMA系粘度指数向上剤A-1」という。)の溶液を得た。
GPC分析(標準物質:ポリスチレン)の結果、得られた非分散型PMA系粘度指数向上剤A-1の重量平均分子量(Mw)は57万、数平均分子量(Mn)は47万、分散度(Mw/Mn)は1.23、PSSIは3.8、Mw/PSSIは1.5×105であった。また、非分散型PMA系粘度指数向上剤A-1のアーム転化率は64質量%、平均アーム数は8本、分岐度は3.0であった。
ここで、アーム転化率及び平均アーム数はそれぞれ以下の式に基いて算出される値である。
アーム転化率=星形高分子のGPC面積/(星形高分子のGPC面積+残存アーム分子のGPC面積)×100
平均アーム数=星型高分子のMn/アーム分子のMn(小数点以下は四捨五入)
また、重量平均分子量及び数平均分子量は、東ソー社製HLC-8220GPC装置に東ソー社製のTSKgel Super MultiPore HZ-Mのカラム(4.6mmID×15cm)を3本直列に使用し、溶媒としてはテトラヒドロフラン、温度40℃、流速0.35mL/分、試料濃度1質量%、試料注入量5μL、検出器示差屈折率計(RI)で測定したポリスチレン換算の重量平均分子量及び数平均分子量である。
合成例1のアーム分子溶液に代えて、メチルメタクリレート70モル%、一般式(4)中のR4が炭素数18のアルキル基であるメタクリレート30モル%のアーム分子(重量平均分子量54000、数平均分子量(Mn)42000、分散度(Mw/Mn)1.29)を含有するアーム分子溶液を用いたこと以外は、合成例1と同様にして、星型高分子(以下、「非分散型PMA系粘度指数向上剤A-2」という。)を合成した。
得られた非分散型PMA系粘度指数向上剤A-2のMwは49万、Mnは41万、Mw/Mnは1.19、PSSIは2.2、Mw/PSSIは2.2×105、分岐度は3.9であった。
合成例1のアーム分子溶液に代えて、メチルメタクリレート70モル%、一般式(4)中のR4が炭素数18のアルキル基であるメタクリレート30モル%のアーム分子(重量平均分子量85000、数平均分子量(Mn)60000、分散度(Mw/Mn)1.42)を含有するアーム分子溶液を用いたこと以外は、合成例1と同様にして、星型高分子(以下、「非分散型PMA系粘度指数向上剤A-3」という。)を合成した。
得られた非分散型PMA系粘度指数向上剤A-3のMwは45万、Mnは38万、Mw/Mnは1.19、PSSIは3.0、Mw/PSSIは1.5×105、分岐度は2.0であった。
実施例1~5および比較例1~4においては、それぞれ以下に示す基油および添加剤を用いて表2に示す組成を有する潤滑油組成物を調製した。基油O-1、O-2、O-3の性状を表1に示す。
(基油)
O-1(基油1):n-パラフィン含有油を水素化分解/水素化異性化した鉱油
O-2(基油2):水素化分解鉱油
O-3(基油3):水素化分解鉱油
(添加剤)
A-1:非分散型PMA系粘度指数向上剤(メチルメタアクリレート70モル%と、一般式(3)中のR2が炭素数18のアルキル基であるメタアクリレート30モル%と、少量の重合開始剤、グリコールジメタクリレートを反応させて得られる共重合体。Mw=57万,Mn=47万,Mw/Mn=1.23,PSSI=3.8,Mw/PSSI=1.5×105,分岐度=3.0)
A-2:非分散型PMA系粘度指数向上剤(メチルメタアクリレート70モル%と、一般式(3)中のR2が炭素数18のアルキル基であるメタアクリレート30モル%と、少量の重合開始剤、グリコールジメタクリレートを反応させて得られる共重合体。Mw=49万,Mn=41万,Mw/Mn=1.19,PSSI=2.2,Mw/PSSI=2.2×105,分岐度=3.9)
A-3:非分散型PMA系粘度指数向上剤(メチルメタアクリレート70モル%と、一般式(3)中のR2が炭素数18のアルキル基であるメタアクリレート30モル%と、少量の重合開始剤、グリコールジメタクリレートを反応させて得られる共重合体。Mw=45万,Mn=38万,Mw/Mn=1.19,PSSI=3.0,Mw/PSSI=1.5×105,分岐度=2.0)
a-1:非分散型PMA系粘度指数向上剤(メチルメタアクリレート70モル%と、一般式(3)中のR2が炭素数18のアルキル基であるメタアクリレート30モル%と、少量の重合開始剤、グリコールジメタクリレートを反応させて得られる共重合体。Mw=62万,Mn=44万,Mw/Mn=1.41,PSSI=5.7,Mw/PSSI=1.1×105,分岐度=9.0)
a-2:分散型PMA系粘度指数向上剤(メチルメタアクリレート20モル%と、一般式(3)中のR2が炭素数12~15のアルキル基であるメタアクリレート80モル%と、少量の分散基および重合開始剤を反応させて得られる共重合体。Mw=30万,Mn=7万,Mw/Mn=4.0,PSSI=40,Mw/PSSI=7.5×103,分岐度=0)
a-3:分散型PMA系粘度指数向上剤(メチルメタアクリレート20モル%と、一般式(3)中のR2が炭素数12~15のアルキル基であるメタアクリレート80モル%と、少量の分散基および重合開始剤を反応させて得られる共重合体。Mw=8万,Mn=3万,Mw/Mn=2.7,PSSI=10,Mw/PSSI=8.0×103,分岐度=0)
B-1:MoDTC(アルキル基鎖長C8/C13、Mo含有量10mass%、硫黄量11mass%)
B-2:グリセリンモノオレート
C-1:その他添加剤(コハク酸イミド系分散剤、ZnDTP、酸化防止剤、摩耗防止剤、流動点降下剤、消泡剤等)。
実施例1~4および比較例1~3の各潤滑油組成物について、40℃または100℃における動粘度、粘度指数、100℃または150℃におけるHTHS粘度、超音波せん断試験後の粘度低下率を測定した。
(1)動粘度:ASTM D-445
(2)粘度指数:JIS K 2283-1993
(3)HTHS粘度:ASTM D-4683
(4)超音波せん断試験:JASO M347-95に準拠し、ASTMの試験法に規定されている標準油Aにて出力調整を行った後、振幅28μm、振動数10KHz、照射時間10分、試料容量を60mLによりせん断試験を実施し、100℃動粘度を測定し、粘度低下率を算出した。
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WO2016043195A1 (ja) * | 2014-09-17 | 2016-03-24 | 株式会社日本触媒 | 粘度指数向上剤及びその製造方法、並びに潤滑油組成物 |
WO2018056316A1 (ja) * | 2016-09-21 | 2018-03-29 | 株式会社日本触媒 | 粘度指数向上剤および潤滑油組成物 |
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WO2015146396A1 (ja) * | 2014-03-24 | 2015-10-01 | Jx日鉱日石エネルギー株式会社 | エンジン油組成物 |
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WO2016043195A1 (ja) * | 2014-09-17 | 2016-03-24 | 株式会社日本触媒 | 粘度指数向上剤及びその製造方法、並びに潤滑油組成物 |
JPWO2016043195A1 (ja) * | 2014-09-17 | 2017-06-01 | 株式会社日本触媒 | 粘度指数向上剤及びその製造方法、並びに潤滑油組成物 |
US10443013B2 (en) | 2014-09-17 | 2019-10-15 | Nippon Shokubai Co., Ltd. | Viscosity index improver, method for producing the same and lubricating oil composition |
WO2018056316A1 (ja) * | 2016-09-21 | 2018-03-29 | 株式会社日本触媒 | 粘度指数向上剤および潤滑油組成物 |
US10982167B2 (en) | 2016-09-21 | 2021-04-20 | Nippon Shokubai Co., Ltd. | Viscosity index improver and lubricating oil composition |
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US20150184109A1 (en) | 2015-07-02 |
CN104487553B (zh) | 2016-12-28 |
JP6129173B2 (ja) | 2017-05-17 |
CN104487553A (zh) | 2015-04-01 |
EP2878658A4 (en) | 2016-03-02 |
EP2878658B1 (en) | 2018-09-05 |
JPWO2014017556A1 (ja) | 2016-07-11 |
EP2878658A1 (en) | 2015-06-03 |
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