WO2022039105A1 - Lubricating oil composition, shock absorber, and method for using lubricating oil composition - Google Patents
Lubricating oil composition, shock absorber, and method for using lubricating oil composition Download PDFInfo
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- WO2022039105A1 WO2022039105A1 PCT/JP2021/029794 JP2021029794W WO2022039105A1 WO 2022039105 A1 WO2022039105 A1 WO 2022039105A1 JP 2021029794 W JP2021029794 W JP 2021029794W WO 2022039105 A1 WO2022039105 A1 WO 2022039105A1
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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
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
- C10M157/10—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a compound containing atoms of elements not provided for in groups C10M157/02 - C10M157/08
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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
- 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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- 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
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, 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
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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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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- 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
- C10N2020/017—Specific gravity or density
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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
- C10N2020/04—Molecular weight; Molecular weight distribution
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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
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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
- C10N2030/08—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
- C10N2030/68—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
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
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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
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- the present invention relates to a lubricating oil composition, a shock absorber using the lubricating oil composition, and a method of using the lubricating oil composition.
- the shock absorber (shock absorber) is used by filling it with a lubricant composition for a shock absorber to generate a damping force that damps the vibration of the vehicle body, and optimizes the friction characteristics of the sliding parts to improve the riding comfort of the vehicle body. It is a mechanism mounted on the vehicle body for the purpose of controlling and suppressing frictional wear of sliding parts to ensure durability.
- Various buffer lubricating oil compositions that can be suitably used for such shock absorbers have been developed.
- Patent Document 1 describes a non-dispersive poly (meth) acrylate-based viscosity modifier having a weight average molecular weight of 30,000 to 200,000 in a lubricating base oil having a predetermined kinematic viscosity, a primary dialkyl.
- An invention relating to a lubricant composition for a shock absorber containing zinc dithiophosphate and secondary zinc dialkyldithiophosphate in a predetermined content ratio is disclosed.
- the lubricating oil composition described in Patent Document 1 has an insufficient effect of suppressing cavitation. Further, there is a demand for a lubricating oil composition used for lubricating a shock absorber having improved characteristics such as low temperature startability and shear stability as well as an effect of suppressing cavitation.
- the present invention provides a lubricating oil composition used for lubricating a shock absorber, which contains a base oil, a polyalkyl (meth) acrylate having a predetermined weight average molecular weight, and an olefin copolymer having a predetermined weight average molecular weight. .. Specifically, the present invention provides the following aspects [1] to [10]. [1] A base oil (A), a polyalkyl (meth) acrylate (B) having a weight average molecular weight of 150,000 to 900,000, and an olefin copolymer (C) having a weight average molecular weight of 100,000 or less. A lubricating oil composition that contains and is used to lubricate shock absorbers.
- the lubricating oil composition of one preferred embodiment of the present invention is excellent in properties such as low temperature startability, shear stability, and cavitation suppressing effect, and a particularly suitable one aspect of the lubricating oil composition is low temperature startability. Since it is excellent in all of the shear stability and the effect of suppressing cavitation, it can be suitably applied to the lubrication of a shock absorber.
- kinematic viscosity and viscosity index mean values measured or calculated in accordance with JIS K2283: 2000.
- weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and are specifically described in Examples. Means the value measured by the method.
- the upper limit value and the lower limit value can be arbitrarily combined.
- the numerical range is described as “preferably 30 to 100, more preferably 40 to 80”
- the range of "30 to 80” and the range of "40 to 100” are also described in the present specification. It is included in the numerical range.
- the numerical range is described as "preferably 30 or more, more preferably 40 or more, preferably 100 or less, more preferably 80 or less”
- the range and the range of "40-100” are also included in the numerical range described herein.
- the description of "60 to 100” means that the range is "60 or more and 100 or less”.
- the lubricating oil composition of the present invention contains a base oil (A), a polyalkyl (meth) acrylate (B) having a weight average molecular weight of 150,000 to 900,000, and an olefin having a weight average molecular weight of 100,000 or less. Contains the polymer (C).
- Various properties are required for the lubricating oil composition in which the shock absorber is used. As one of such characteristics, the effect of suppressing cavitation is required.
- Cavitation is a physical phenomenon in which bubbles are generated and disappear in a short time due to a pressure difference in the flow of a lubricating oil composition, and is a factor that causes a decrease in the responsiveness of the shock absorber and noise.
- the lubricating oil composition in which the shock absorber is used is required to have not only the effect of suppressing cavitation but also the characteristics such as low temperature startability and shear stability.
- the present inventors have diligently studied in order to obtain a lubricating oil composition capable of improving these properties in a well-balanced manner, and as a result, polyalkyl (meth) acrylate (B) and an olefin copolymer having a predetermined weight average molecular weight ( C) was found to be useful in combination. That is, the component (B) is a factor that can improve the cavitation suppressing effect and the low temperature startability, but is a factor that causes a decrease in the shear stability, while the component (C) is a factor that suppresses the cavitation and the shear stability.
- the components (B) and the component (C) are used from the viewpoint of providing a lubricating oil composition having improved low temperature startability, shear stability, and cavitation suppressing effect in a well-balanced manner.
- the content ratio [(B) / (C)] is preferably 1/99 to 90/10, more preferably 5/85 to 80/20, and more preferably 10/90 to 70/30 in terms of mass ratio. , More preferably 15/85 to 60/40, even more preferably 20/80 to 50/50, and particularly preferably 25/75 to 45/55.
- the total content of the component (B) and the component (C) is based on the total amount (100% by mass) of the lubricating oil composition, and has low-temperature startability and shear stability.
- it is preferably 20.0% by mass or less, more preferably 16.0% by mass or less, still more preferably 10.0% by mass or less, still more preferably 8.
- It is 0.0% by mass or less, particularly preferably 6.0% by mass or less, and from the viewpoint of further improving the effect of suppressing cavitation, it is preferably 0.2% by mass or more, more preferably 0.6% by mass or more. It is more preferably 1.0% by mass or more, still more preferably 1.6% by mass or more, and particularly preferably 2.0% by mass or more.
- the components (B) and (C) are often marketed in the form of a solution dissolved in a diluted oil.
- the content of the component (B) and (C) is the resin constituting the component (B) or (C) excluding the mass of the diluted oil in the solution diluted with the diluted oil. It is the content converted into minutes.
- the lubricating oil composition of one aspect of the present invention may further contain additives for lubricating oil other than the components (B) to (C).
- the total content of the components (A) to (C) is determined from the viewpoint of making the lubricating oil composition further improved in the effect of suppressing cavitation and the low temperature startability. Based on the total amount (100% by mass) of the lubricating oil composition, it is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.
- it is 98 to 100% by mass, and more than 98.5% by mass and 100% by mass or less, 99.0% by mass and 100% by mass or less, 99.5% by mass and 100% by mass or less, or 99. It may be more than 7% by mass and 100% by mass or less.
- Base oil examples include one or more selected from mineral oils and synthetic oils.
- Mineral oils include, for example, normal pressure residual oil obtained by atmospheric distillation of crude oils such as paraffin crude oil, intermediate base crude oil, and naphthenic crude oil; and distillate oil obtained by vacuum distillation of these normal pressure residual oils. ; Refined oil obtained by subjecting the distillate oil to one or more refining treatments such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining; and the like.
- Examples of the synthetic oil include poly ⁇ -olefins such as ⁇ -olefin homopolymers; isoparaffin; polyalkylene glycols; ester oils such as polyol esters, dibasic acid esters and phosphate esters; ether oils such as polyphenyl ethers. Oil; Alkylbenzene; Alkylnaphthalene; Synthetic oil (GTL) obtained by isomerizing a wax (GTL wax (Gas To Liquids WAX)) produced from natural gas by the Fischer-Tropsch method or the like can be mentioned.
- GTL wax Gas To Liquids WAX
- the component (A) used in one embodiment of the present invention includes mineral oils classified into Group 2 and Group 3 of the API (American Petroleum Institute) base oil category, and one or more selected from synthetic oils. Is preferable.
- the kinematic viscosity of the component (A) used in one aspect of the present invention at 40 ° C. is preferably 3.0 to 100 mm 2 / s, more preferably 4.0 to 70 mm 2 / s, still more preferably 5.0 to 40 mm. It is 2 / s, more preferably 5.5 to 30 mm 2 / s, and particularly preferably 6.0 to 20 mm 2 / s.
- the viscosity index of the component (A) used in one aspect of the present invention is appropriately set according to the use of the lubricating oil composition, but is preferably 70 or more, more preferably 80 or more, still more preferably 90 or more. It is even more preferably 100 or more, and particularly preferably 105 or more.
- the kinematic viscosity and the viscosity index of the mixed oil are preferably in the above ranges.
- the content of the component (A) is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total amount (100% by mass) of the lubricating oil composition. , More preferably 75% by mass or more, further preferably 80% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and preferably 99.8% by mass or less, more preferably. It is 99.5% by mass or less, more preferably 99.0% by mass or less, still more preferably 98.5% by mass or less, and particularly preferably 98.0% by mass or less.
- the lubricating oil composition of the present invention contains a polyalkyl (meth) acrylate having a weight average molecular weight (Mw) of 150,000 to 900,000 as the component (B). If Mw is less than 150,000, the effect of suppressing cavitation is less likely to be exhibited. Further, when Mw is larger than 900,000, it tends to be difficult to achieve both the cavitation suppressing effect and the shear stability. Since the component (C) described later is used in combination with the component (B), the lubricating oil composition can be adjusted to have good shear stability.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) of the polyalkyl (meth) acrylate used as the component (B) in one aspect of the present invention is 150,000 or more, but the lubricating oil has further improved the effect of suppressing cavitation and the low temperature startability. From the viewpoint of the composition, it is preferably 200,000 or more, more preferably 250,000 or more, more preferably 260,000 or more, more preferably 270,000 or more, more preferably 300,000 or more, still more preferably 320. 000 or more, more preferably 350,000 or more, still more preferably 370,000 or more, still more preferably 400,000 or more, still more preferably 420,000 or more, still more preferably 450,000 or more, still more preferably.
- It is 470,000 or more, more preferably 500,000 or more, particularly preferably 520,000 or more, and 900,000 or less, but from the viewpoint of obtaining a lubricating oil composition having better shear stability. It is preferably 850,000 or less, more preferably 800,000 or less, more preferably 750,000 or less, still more preferably 700,000 or less, still more preferably 650,000 or less, and particularly preferably 600,000 or less. ..
- the content of the component (B) is based on the total amount (100% by mass) of the lubricating oil composition, and the lubricating effect of suppressing cavitation and the low-temperature startability are further improved.
- it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably.
- the component (B) used in one embodiment of the present invention may be a polymer having a structural unit derived from an alkyl acrylate or an alkyl methacrylate (hereinafter collectively referred to as “alkyl (meth) acrylate”), and may be an alkyl (meth). ) It may be a copolymer having a structural unit derived from a monomer other than acrylate.
- the number of carbon atoms of the alkyl group contained in the alkyl (meth) acrylate may be 1 or more, 3 or more, 5 or more, or 10 or more, and may be 60 or less, 40 or less, 30 or less, or 20 or less.
- the content of the structural unit derived from the alkyl (meth) acrylate is 10 mol% or more based on the total amount (100 mol%) of the structural unit of the component (B). It may be 30 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more.
- the component (B) used in one embodiment of the present invention may be a comb-shaped polymer.
- the comb-shaped polymer used as the component (B) in one aspect of the present invention may be a polymer having a structure having a large number of three-pronged branch points in the main chain having high molecular weight side chains.
- the SSI (shear stability index) of the comb polymer used as the component (B) in one aspect of the present invention is preferably 100 or less, more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, particularly. It is preferably 50 or less. Further, the SSI of the comb polymer is not particularly limited to the lower limit value, but is usually 0.1 or more.
- the SSI shear stability index
- SSI (%) (Kv 0 -Kv 1 ) / (Kv 0 -Kv oil ) x 100
- Kv 0 is the value of the kinematic viscosity of the sample oil obtained by diluting the polymer component with mineral oil at 100 ° C.
- Kv 1 is the sample oil obtained by diluting the polymer component with mineral oil.
- Kv oil is a value of the kinematic viscosity of the mineral oil used for diluting the polymer component at 100 ° C.
- the SSI value of the comb polymer varies depending on its structure. Specifically, there is a tendency shown below, and the value of SSI of the comb-shaped polymer can be easily adjusted by considering these matters. The following items are just examples and can be adjusted by considering items other than these items.
- the side chain of the comb-shaped polymer is composed of a macromonomer (x1), and the content of the structural unit (X1) derived from the macromonomer (x1) is 0.5 based on the total amount (100 mol%) of the structural unit.
- Comb-shaped polymers of mol% or more tend to have lower SSI values.
- the larger the molecular weight of the macromonomer (x1) constituting the side chain of the comb-shaped polymer the lower the SSI value tends to be.
- the comb-shaped polymer used as the component (B) in one aspect of the present invention is preferably a polymer having at least a structural unit (X1) derived from the macromonomer (x1).
- This structural unit (X1) corresponds to the above-mentioned "high molecular weight side chain".
- the above-mentioned "macromonomer (x1)” means a high molecular weight monomer having a polymerizable functional group, and is preferably a high molecular weight monomer having a polymerizable functional group at the terminal. ..
- the content of the constituent unit (X1) is preferably 0.5 to 20 mol based on the total amount (100 mol%) of the constituent units of the comb polymer. %, More preferably 0.7 to 10 mol%, still more preferably 0.9 to 5 mol%.
- the content of the constituent unit of the comb-shaped polymer means a value calculated by analyzing the 13 C-NMR quantitative spectrum.
- the number average molecular weight (Mn) of the macromonomer (x1) is preferably 300 or more, more preferably 400 or more, still more preferably 500 or more, and preferably 100,000 or less, more preferably 50,000 or less. , More preferably 20,000 or less. That is, the number average molecular weight (Mn) of the macromonomer (x1) is preferably 300 to 100,000, more preferably 400 to 50,000, and even more preferably 500 to 20,000.
- the macromonomer (x1) may have, for example, one or more repeating units represented by the following general formulas (i) to (iii) in addition to the above-mentioned polymerizable functional group.
- R b1 is a linear or branched alkylene group having 1 to 10 carbon atoms.
- R b2 is a linear or branched alkylene group having 2 to 4 carbon atoms.
- R b3 is a hydrogen atom or a methyl group.
- R b4 is a linear or branched alkyl group having 1 to 10 carbon atoms.
- the macromonomer (x1) is preferably a polymer having a repeating unit represented by the general formula (i), and R b1 in the general formula (i) is 1,2.
- -A polymer having a repeating unit (X1-1) which is at least one of a butylene group and a 1,4-butylene group is more preferable.
- the content of the repeating unit (X1-1) is preferably 1 to 100 mol%, more preferably 20 to 95 mol%, still more preferably, based on the total amount (100 mol%) of the constituent units of the macromonomer (x1). Is 40 to 90 mol%, more preferably 50 to 80 mol%.
- the macromonomer (x1) is a copolymer having two or more repeating units selected from the general formulas (i) to (iii)
- the form of copolymerization is a block copolymer. It may be a random copolymer or a random copolymer.
- the comb-shaped polymer used as the component (B) in one aspect of the present invention may be a homopolymer consisting of only a structural unit (X1) derived from one type of macromonomer (x1), or two or more types of macromonomers (x1). It may be a copolymer having a structural unit (X1) derived from. Further, the comb-shaped polymer used as the component (B) in one aspect of the present invention has a structural unit (X1) derived from the macromonomer (x1) and a structural unit (X2) derived from a monomer other than the macromonomer (x1). ) May be a copolymer.
- a main chain containing a structural unit (X2) derived from a monomer (x2) is opposed to a side chain containing a structural unit (X1) derived from a macromonomer (x1).
- a copolymer having the above is preferable.
- Examples of the monomer (x2) include an alkyl (meth) acrylate, a nitrogen atom-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, a phosphorus atom-containing monomer, an aliphatic hydrocarbon-based vinyl monomer, and an alicyclic type.
- Hydrocarbon-based vinyl monomers, vinyl esters, vinyl ethers, vinyl ketones, epoxy group-containing vinyl monomers, halogen element-containing vinyl monomers, unsaturated polycarboxylic acid esters, (di) alkyl fumarate, ( D) Alkyl maleate, aromatic hydrocarbon-based vinyl monomer and the like can be mentioned.
- the monomer (x2) is preferably a monomer other than the phosphorus atom-containing monomer and the aromatic hydrocarbon-based vinyl monomer, and the monomer represented by the following general formula (a1), alkyl (meth). ) It is more preferable to contain at least one selected from acrylate and a hydroxyl group-containing vinyl monomer, and further preferably to contain at least a hydroxyl group-containing vinyl monomer (x2-d).
- R b11 is a hydrogen atom or a methyl group.
- R b12 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, -O-, or -NH-.
- R b13 is a linear or branched alkylene group having 2 to 4 carbon atoms.
- n represents an integer of 1 or more (preferably an integer of 1 to 20, more preferably an integer of 1 to 5).
- the plurality of R b13s may be the same or different, and the (R b13 O) n portion may be a random bond or a block bond.
- R b14 is a linear or branched alkyl group having 1 to 60 carbon atoms (preferably 10 to 50, more preferably 20 to 40).
- the lubricating oil composition of the present invention contains an olefin copolymer having a weight average molecular weight (Mw) of 100,000 or less as the component (C).
- Mw weight average molecular weight
- a lubricating oil composition having an improved cavitation suppressing effect and shear stability can be obtained. Since the above-mentioned component (B) is used in combination with the component (C), the lubricating oil composition can be adjusted to have good low-temperature startability.
- the weight average molecular weight (Mw) of the olefin copolymer used as the component (C) in one aspect of the present invention is 100,000 or less, but the low temperature startability and shear stability are improved while further improving the effect of suppressing cavitation. From the viewpoint of obtaining a better lubricating oil composition, preferably 80,000 or less, more preferably 70,000 or less, more preferably 60,000 or less, still more preferably 40,000 or less, still more preferably 30. It is 000 or less, particularly preferably 25,000 or less.
- the weight average molecular weight (Mw) of the olefin copolymer as the component (C) is 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 7,000 or more, 8,000 or more, 8. It may be over 000, 8,000 or more, 9,000 or more, 9,500 or more, 10,000 or more, 11,000 or more, 12,000 or more, or 13,000 or more.
- the content of the component (C) is based on the total amount (100% by mass) of the lubricating oil composition, and the effect of suppressing cavitation and the shear stability are further improved.
- it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and particularly preferably.
- the component (C) used in one embodiment of the present invention is a copolymer having a structural unit derived from a monomer having an alkenyl group, and is, for example, a copolymer having 2 to 20 carbon atoms (preferably 2 to 16 carbon atoms, more preferably 2 to 16 carbon atoms). Examples thereof include the ⁇ -olefin copolymers of 2 to 14), and more specifically, the ethylene- ⁇ -olefin copolymer is preferable.
- the number of carbon atoms of the ⁇ -olefin constituting the ethylene- ⁇ -olefin copolymer is preferably 3 to 20, more preferably 3 to 16, still more preferably 3 to 14, and even more preferably 3. ⁇ 6, particularly preferably 3.
- the component (C) used in one aspect of the present invention may be a dispersed olefin-based copolymer.
- a dispersed olefin-based copolymer a copolymer obtained by graft-polymerizing the above-mentioned ethylene- ⁇ -olefin copolymer with maleic acid, N-vinylpyrrolidone, N-vinylimidazole, glycidyl acrylate and the like. Can be mentioned.
- the component (C) used in one embodiment of the present invention may be a copolymer having a structural unit derived from a monomer having an alkenyl group and further having a structural unit derived from an aromatic monomer.
- examples of such an olefin-based copolymer include styrene-based copolymers such as a styrene-diene copolymer and a styrene-isoprene copolymer.
- the component (C) used in one aspect of the present invention may contain an ethylene propylene copolymer (C1) from the viewpoint of obtaining a lubricating oil composition having an effect of suppressing cavitation and improved shear stability.
- the content ratio of the component (C1) is preferably 30 to 100% by mass with respect to the total amount (100% by mass) of the component (C) contained in the lubricating oil composition. %, More preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.
- the lubricating oil composition of one aspect of the present invention may further contain an additive for lubricating oil other than the component (B) and the component (C), if necessary, as long as the effect of the present invention is not impaired.
- additives for lubricating oil include antioxidants such as phenol-based antioxidants and amino-based antioxidants; metal-based detergents such as metal sulfonates, metal salicylates, and metal phenates; alkenyl succinate imide and the like.
- Ash-free dispersant Molybdenum-based friction modifier, fatty acid ester, fatty acid, friction modifier such as aliphatic alcohol; Abrasion resistant agent such as zinc dithiophosphate; Phosphorus-based extreme pressure agent, sulfur-based extreme pressure agent, sulfur- Extreme pressure agents such as phosphorus-based extreme pressure agents; defoaming agents such as silicone-based defoaming agents; metal inactivating agents such as benzotriazole-based compounds; rust preventives; antistatic agents; and the like. These lubricant additives may be used alone or in combination of two or more.
- each of these additives for lubricating oil can be appropriately prepared within a range that does not impair the effects of the present invention, but each addition is based on the total amount (100% by mass) of the lubricating oil composition. Independently for each agent, it is usually 0.001 to 15% by mass, preferably 0.005 to 10% by mass, and more preferably 0.01 to 5% by mass.
- the method for producing the lubricating oil composition according to one aspect of the present invention is not particularly limited, but from the viewpoint of productivity, the component (A) includes the component (B) and the component (C), and if necessary. , It is preferable that the method has a step of blending other additives for lubricating oil.
- the resin components such as the component (B) and the component (C) are in the form of a solution dissolved in the diluted oil from the viewpoint of compatibility with the component (A), and the solution is blended with the component (A). Is preferable.
- the kinematic viscosity of the lubricating oil composition of one aspect of the present invention at 40 ° C. is preferably 5.0 to 130 mm 2 / s, more preferably 6.5 to 100 mm 2 / s, still more preferably 8.0 to 100 mm 2 . / S, more preferably 10.0 to 60 mm 2 / s, and particularly preferably 11.0 to 40 mm 2 / s.
- the kinematic viscosity of the lubricating oil composition of one aspect of the present invention at 100 ° C. is preferably 2.0 to 30 mm 2 / s, more preferably 2.3 to 20 mm 2 / s, still more preferably 2.6 to 15 mm 2 . / S, more preferably 3.0 to 10 mm 2 / s, and particularly preferably 3.2 to 7.0 mm 2 / s.
- the kinematic viscosity of the lubricating oil composition of one aspect of the present invention at 150 ° C. is preferably 1.0 to 20 mm 2 / s, more preferably 1.2 to 10 mm 2 / s, and even more preferably 1.4 to 7. It is 0 mm 2 / s, more preferably 1.6 to 5.0 mm 2 / s, and particularly preferably 1.8 to 3.0 mm 2 / s.
- the viscosity index of the lubricating oil composition according to one aspect of the present invention is preferably 100 or more, more preferably 120 or more, still more preferably 140 or more, still more preferably 160 or more, and particularly preferably 180 or more.
- the BF viscosity (Brookfield viscosity) of the lubricating oil composition according to one aspect of the present invention at ⁇ 40 ° C. is preferably 1500 mPa ⁇ s or less, more preferably 1400 mPa, from the viewpoint of obtaining a lubricating oil composition having good low-temperature startability.
- -S or less more preferably 1300 mPa ⁇ s or less, still more preferably 1200 mPa ⁇ s or less, preferably 100 mPa ⁇ s or more, more preferably 300 mPa ⁇ s or more, still more preferably 500 mPa ⁇ s or more, still more. It is preferably 700 mPa ⁇ s or more.
- the BF viscosity means a value measured according to ASTM D2983-09.
- the rate of decrease in kinematic viscosity calculated according to the method described in Examples described later for the lubricating oil composition of one aspect of the present invention is preferably 11 from the viewpoint of obtaining a lubricating oil composition having good shear stability. It is less than 0.0%, more preferably less than 10.5%, even more preferably less than 10.0%, still more preferably less than 9.5%.
- the value of the cavitation coefficient calculated according to the method described in Examples described later for the lubricating oil composition of one aspect of the present invention is preferably from the viewpoint of obtaining a lubricating oil composition having an excellent effect of suppressing cavitation. It is 0.45 or less, more preferably 0.44 or less, still more preferably 0.43 or less, and usually 0.40 or more.
- the lubricating oil composition of one aspect of the present invention has excellent properties such as low temperature startability, shear stability, and cavitation suppressing effect. Therefore, the lubricating oil composition according to one aspect of the present invention can be suitably used for lubricating a shock absorber, and more specifically, it can be used for both a double-cylinder shock absorber and a single-cylinder shock absorber. , Can be suitably used for both two-wheeled and four-wheeled shock absorbers. Considering these properties of the lubricating oil composition of one aspect of the present invention, the present invention may also provide the following [1] and [2].
- a shock absorber filled with the above-mentioned lubricating oil composition according to one aspect of the present invention [1] A shock absorber filled with the above-mentioned lubricating oil composition according to one aspect of the present invention. [2] Use of a lubricating oil composition, which applies the above-mentioned lubricating oil composition of one aspect of the present invention to lubricate a shock absorber.
- Example 1 Comparative Examples 1 to 8 Various additives were blended with the base oil according to the types and blending amounts shown in Table 1, and lubricating oil compositions were prepared respectively.
- the blending amounts of the various additives shown in Table 1 are the blending amounts in terms of active ingredients (solid content equivalent) excluding the mass of the diluted oil, even if they are blended in a state of being dissolved in the diluted oil. It is described.
- the details of the base oil and various additives used for preparing each lubricating oil composition are as follows.
- PMA> "PMA (550,000)”: Polyalkyl (meth) acrylate having a weight average molecular weight (Mw) 550,000.
- PMA (29,000) Polyalkyl (meth) acrylate having a weight average molecular weight (Mw) of 29,000.
- the prepared lubricating oil composition was measured or calculated for 40 ° C. kinematic viscosity, 100 ° C. kinematic viscosity, 150 ° C. kinematic viscosity, and viscosity index, and the following measurements or evaluations were performed. These results are shown in Table 1.
- the shear test is based on the ultrasonic A method (JPI-5S-29), and the prepared lubricating oil composition is used as the sample oil, and ultrasonic waves are applied to 30 mL of the sample oil at 25 ° C. Was irradiated for 60 minutes.
- the output voltage of the ultrasonic wave is 30 mL of standard oil whose kinematic viscosity has been measured in advance at 40 ° C., and the output voltage has a decrease rate of 40 ° C. Adopted the value. Then, the kinematic viscosity of the sample oil at 40 ° C.
- FIG. 1 is a schematic diagram of a test device for evaluating the cavitation suppressing effect.
- the test apparatus 1 shown in FIG. 1 includes an oil tank 11 for storing the sample oil to be evaluated, a pump 12 for circulating the sample oil, a heater 13 for adjusting the temperature of the sample oil, a flow meter 14 for controlling the flow velocity of the sample oil, and a sample.
- Valves 15a, 15b, 15c for controlling oil flow, observation tank 16 with sapphire observation windows on the sides and an orifice 16a with a diameter of 1 mm at the upstream inlet, and pressure on the upstream and downstream sides of the observation tank, respectively. It has a total of 17a, 17b, and a thermoelectric pair 18.
- the prepared lubricating oil composition is filled in the oil tank 11 as sample oil, the valves 15a, 15b, and 15c are fully opened, the pump 12 and the heater 13 are operated, and along the flow path 1 and the flow path 2.
- the observation tank 16 was also filled with the sample oil while circulating the sample oil. Then, the state in which the temperature of the sample oil reached 150 ° C. and was stabilized was set as the initial state. From the initial state, the valve 15c is gradually closed from the fully open state, the flow along the flow path 2 of the sample oil is restricted, and the state where the pressure gauge 17a on the upstream side shows "0.5 MPa" is set as the starting point.
- the valve 15a on the upstream side and the valve 15b on the downstream side were adjusted, and the pressure was gradually increased until the pressure gauge 17a on the upstream side showed "5.0 MPa".
- the degree of cavitation is visually observed through the transparent window of the observation tank 16 based on the cavitation score for which the standard is set in advance according to the degree of cavitation, and cavitation.
- the upstream pressure Pu indicated by the upstream pressure gauge 17a and the downstream pressure Pd indicated by the downstream pressure gauge 17b at the point where the score was "5" were confirmed, and the cavitation coefficient was calculated.
- the above cavitation score is evaluated in 11 steps in 1 increments, with "0" for non-occurrence of cavitation and "10" for the maximum occurrence of cavitation, and the standard for each step is cavitation. Based on what is predetermined according to the degree of occurrence.
- the cavitation coefficient was calculated from the following formula, and the values are shown in Table 1.
- the lubricating oil composition prepared in Example 1 was excellent in low temperature startability and shear stability, and also had a high effect of suppressing cavitation.
- the lubricating oil compositions prepared in Comparative Examples 1 to 8 were inferior in any of the low temperature startability, shear stability, and cavitation suppressing effect.
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Abstract
Description
本発明は、潤滑油組成物、及び当該潤滑油組成物を用いた緩衝器、並びに当該潤滑油組成物の使用方法に関する。 The present invention relates to a lubricating oil composition, a shock absorber using the lubricating oil composition, and a method of using the lubricating oil composition.
緩衝器(ショックアブソーバー)は、緩衝器用潤滑油組成物を充填して使用され、車体の振動を減衰する減衰力を生じさせること、摺動部の摩擦特性を最適化させて車体の乗心地を制御すること、及び摺動部の摩擦摩耗を抑制して耐久性を担保すること等を目的にして車体に搭載される機構である。
このような緩衝器に好適に使用し得る緩衝器用潤滑油組成物が様々開発されている。
例えば、特許文献1には、所定の動粘度の潤滑油基油に、重量平均分子量が30,000~200,000である非分散型のポリ(メタ)アクリレート系粘度調整剤、第一級ジアルキルジチオリン酸亜鉛と、第二級ジアルキルジチオリン酸亜鉛とを所定の含有量比で含有した、緩衝器用潤滑油組成物に関する発明が開示されている。
The shock absorber (shock absorber) is used by filling it with a lubricant composition for a shock absorber to generate a damping force that damps the vibration of the vehicle body, and optimizes the friction characteristics of the sliding parts to improve the riding comfort of the vehicle body. It is a mechanism mounted on the vehicle body for the purpose of controlling and suppressing frictional wear of sliding parts to ensure durability.
Various buffer lubricating oil compositions that can be suitably used for such shock absorbers have been developed.
For example, Patent Document 1 describes a non-dispersive poly (meth) acrylate-based viscosity modifier having a weight average molecular weight of 30,000 to 200,000 in a lubricating base oil having a predetermined kinematic viscosity, a primary dialkyl. An invention relating to a lubricant composition for a shock absorber containing zinc dithiophosphate and secondary zinc dialkyldithiophosphate in a predetermined content ratio is disclosed.
本発明者らの検討によれば、特許文献1に記載の潤滑油組成物は、キャビテーションの抑制効果が不十分であることが分かった。また、キャビテーションの抑制効果と共に、低温始動性及びせん断安定性等の特性を向上させた緩衝器の潤滑に用いられる潤滑油組成物が求められている。 According to the studies by the present inventors, it was found that the lubricating oil composition described in Patent Document 1 has an insufficient effect of suppressing cavitation. Further, there is a demand for a lubricating oil composition used for lubricating a shock absorber having improved characteristics such as low temperature startability and shear stability as well as an effect of suppressing cavitation.
本発明は、基油、所定の重量平均分子量のポリアルキル(メタ)アクリレート、及び、所定の重量平均分子量のオレフィン共重合体を含有する、緩衝器の潤滑に用いられる潤滑油組成物を提供する。具体的には、本発明は、下記態様[1]~[10]を提供する。
[1]基油(A)、重量平均分子量が150,000~900,000のポリアルキル(メタ)アクリレート(B)、及び、重量平均分子量が100,000以下のオレフィン共重合体(C)を含有し、緩衝器の潤滑に用いられる、潤滑油組成物。
[2]成分(B)及び成分(C)の合計含有量が、前記潤滑油組成物の全量基準で、20.0質量%以下である、上記[1]に記載の潤滑油組成物。
[3]成分(B)と成分(C)との含有量比〔(B)/(C)〕が、質量比で、1/99~90/10である、上記[1]又は[2]の記載の潤滑油組成物。
[4]成分(B)の含有量が、前記潤滑油組成物の全量基準で、0.1~10.0質量%である、上記[1]~[3]のいずれか一項に記載の潤滑油組成物。
[5]成分(C)の含有量が、前記潤滑油組成物の全量基準で、0.1~10.0質量%である、上記[1]~[4]のいずれか一項に記載の潤滑油組成物。
[6]成分(C)の重量平均分子量が、8,000以上100,000以下である、上記[1]~[5]のいずれか一項に記載の潤滑油組成物。
[7]成分(C)が、エチレンプロピレン共重合体(C1)を含む、上記[1]~[6]のいずれか一項に記載の潤滑油組成物。
[8]成分(A)~(C)の合計含有量が、前記潤滑油組成物の全量基準で、80~100質量%である、上記[1]~[7]のいずれか一項に記載の潤滑油組成物。
[9]前記潤滑油組成物の-40℃におけるBF粘度が1500mPa・s以下である、上記[1]~[8]のいずれか一項に記載の潤滑油組成物。
[10]上記[1]~[9]のいずれか一項に記載の潤滑油組成物を緩衝器の潤滑に適用する、潤滑油組成物の使用。
The present invention provides a lubricating oil composition used for lubricating a shock absorber, which contains a base oil, a polyalkyl (meth) acrylate having a predetermined weight average molecular weight, and an olefin copolymer having a predetermined weight average molecular weight. .. Specifically, the present invention provides the following aspects [1] to [10].
[1] A base oil (A), a polyalkyl (meth) acrylate (B) having a weight average molecular weight of 150,000 to 900,000, and an olefin copolymer (C) having a weight average molecular weight of 100,000 or less. A lubricating oil composition that contains and is used to lubricate shock absorbers.
[2] The lubricating oil composition according to the above [1], wherein the total content of the component (B) and the component (C) is 20.0% by mass or less based on the total amount of the lubricating oil composition.
[3] The content ratio [(B) / (C)] of the component (B) to the component (C) is 1/99 to 90/10 in terms of mass ratio, as described above [1] or [2]. The lubricating oil composition according to.
[4] The item according to any one of [1] to [3] above, wherein the content of the component (B) is 0.1 to 10.0% by mass based on the total amount of the lubricating oil composition. Lubricating oil composition.
[5] The item according to any one of [1] to [4] above, wherein the content of the component (C) is 0.1 to 10.0% by mass based on the total amount of the lubricating oil composition. Lubricating oil composition.
[6] The lubricating oil composition according to any one of the above [1] to [5], wherein the weight average molecular weight of the component (C) is 8,000 or more and 100,000 or less.
[7] The lubricating oil composition according to any one of the above [1] to [6], wherein the component (C) contains an ethylene propylene copolymer (C1).
[8] The item according to any one of [1] to [7] above, wherein the total content of the components (A) to (C) is 80 to 100% by mass based on the total amount of the lubricating oil composition. Lubricating oil composition.
[9] The lubricating oil composition according to any one of the above [1] to [8], wherein the BF viscosity of the lubricating oil composition at −40 ° C. is 1500 mPa · s or less.
[10] Use of a lubricating oil composition for applying the lubricating oil composition according to any one of the above [1] to [9] to lubricate a shock absorber.
本発明の好適な一態様の潤滑油組成物は、低温始動性、せん断安定性、及びキャビテーションの抑制効果等の特性に優れており、特に好適な一態様の潤滑油組成物は、低温始動性、せん断安定性、及びキャビテーションの抑制効果のいずれにも優れているため、緩衝器の潤滑に好適に適用し得る。 The lubricating oil composition of one preferred embodiment of the present invention is excellent in properties such as low temperature startability, shear stability, and cavitation suppressing effect, and a particularly suitable one aspect of the lubricating oil composition is low temperature startability. Since it is excellent in all of the shear stability and the effect of suppressing cavitation, it can be suitably applied to the lubrication of a shock absorber.
本明細書において、動粘度及び粘度指数は、JIS K2283:2000に準拠して測定又は算出された値を意味する。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法により測定された値を意味する。
As used herein, kinematic viscosity and viscosity index mean values measured or calculated in accordance with JIS K2283: 2000.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and are specifically described in Examples. Means the value measured by the method.
本明細書に記載された数値範囲については、上限値及び下限値を任意に組み合わせることができる。例えば、数値範囲として「好ましくは30~100、より好ましくは40~80」と記載されている場合、「30~80」との範囲や「40~100」との範囲も、本明細書に記載された数値範囲に含まれる。また、例えば、数値範囲として「好ましくは30以上、より好ましくは40以上であり、また、好ましくは100以下、より好ましくは80以下である」と記載されている場合、「30~80」との範囲や「40~100」との範囲も、本明細書に記載された数値範囲に含まれる。
加えて、本明細書に記載された数値範囲として、例えば「60~100」との記載は、「60以上、100以下」という範囲であることを意味する。
For the numerical range described in the present specification, the upper limit value and the lower limit value can be arbitrarily combined. For example, when the numerical range is described as "preferably 30 to 100, more preferably 40 to 80", the range of "30 to 80" and the range of "40 to 100" are also described in the present specification. It is included in the numerical range. Further, for example, when the numerical range is described as "preferably 30 or more, more preferably 40 or more, preferably 100 or less, more preferably 80 or less", it is referred to as "30 to 80". The range and the range of "40-100" are also included in the numerical range described herein.
In addition, as the numerical range described in the present specification, for example, the description of "60 to 100" means that the range is "60 or more and 100 or less".
〔潤滑油組成物の構成〕
本発明の潤滑油組成物は、基油(A)、重量平均分子量が150,000~900,000のポリアルキル(メタ)アクリレート(B)、及び、重量平均分子量が100,000以下のオレフィン共重合体(C)を含有する。
緩衝器の用いられる潤滑油組成物には、様々な特性が要求される。そのような特性の一つとして、キャビテーションの抑制効果が求められる。キャビテーションとは、潤滑油組成物の流れの中で圧力差により短時間に泡の発生と消滅が起きる物理現象であり、緩衝器の応答性の低下や騒音を引き起こす要因となる。例えば、車両に搭載された緩衝器において、キャビテーションが発生すると、車両等の乗り心地に影響を及ぼす。
また、緩衝器の用いられる潤滑油組成物には、キャビテーションの抑制効果だけでなく、低温始動性やせん断安定性といった特性も要求される。
[Structure of lubricating oil composition]
The lubricating oil composition of the present invention contains a base oil (A), a polyalkyl (meth) acrylate (B) having a weight average molecular weight of 150,000 to 900,000, and an olefin having a weight average molecular weight of 100,000 or less. Contains the polymer (C).
Various properties are required for the lubricating oil composition in which the shock absorber is used. As one of such characteristics, the effect of suppressing cavitation is required. Cavitation is a physical phenomenon in which bubbles are generated and disappear in a short time due to a pressure difference in the flow of a lubricating oil composition, and is a factor that causes a decrease in the responsiveness of the shock absorber and noise. For example, when cavitation occurs in a shock absorber mounted on a vehicle, it affects the ride quality of the vehicle or the like.
Further, the lubricating oil composition in which the shock absorber is used is required to have not only the effect of suppressing cavitation but also the characteristics such as low temperature startability and shear stability.
本発明者らは、これらの特性をバランス良く向上し得る潤滑油組成物とするために鋭意検討したところ、所定の重量平均分子量を有するポリアルキル(メタ)アクリレート(B)及びオレフィン共重合体(C)を組み合わせが有用であることを見出した。
つまり、成分(B)は、キャビテーションの抑制効果及び低温始動性を向上させ得る要因となるが、せん断安定性の低下を引き起こす要因となり、一方、成分(C)は、キャビテーションの抑制効果及びせん断安定性を向上させ得る要因となるが、低温始動性の低下を引き起こす要因となることが、本発明者らの検討によって分かった。
そこで、本発明者らは、成分(B)及び(C)を併用することで、低温始動性、せん断安定性、及びキャビテーションの抑制効果をバランス良く向上させた潤滑油組成物となり得るとの知見を得た。本発明は、当該知見に基づき完成されたものである。
The present inventors have diligently studied in order to obtain a lubricating oil composition capable of improving these properties in a well-balanced manner, and as a result, polyalkyl (meth) acrylate (B) and an olefin copolymer having a predetermined weight average molecular weight ( C) was found to be useful in combination.
That is, the component (B) is a factor that can improve the cavitation suppressing effect and the low temperature startability, but is a factor that causes a decrease in the shear stability, while the component (C) is a factor that suppresses the cavitation and the shear stability. Although it is a factor that can improve the property, it has been found by the studies of the present inventors that it is a factor that causes a decrease in low-temperature startability.
Therefore, the present inventors have found that by using the components (B) and (C) in combination, a lubricating oil composition having a well-balanced improvement in low temperature startability, shear stability, and cavitation suppressing effect can be obtained. Got The present invention has been completed based on this finding.
本発明の一態様の潤滑油組成物において、低温始動性、せん断安定性、及びキャビテーションの抑制効果をバランス良く向上させた潤滑油組成物とする観点から、成分(B)と成分(C)との含有量比〔(B)/(C)〕は、質量比で、好ましくは1/99~90/10、より好ましくは5/85~80/20、より好ましくは10/90~70/30、更に好ましくは15/85~60/40、より更に好ましくは20/80~50/50、特に好ましくは25/75~45/55である。 In the lubricating oil composition of one aspect of the present invention, the components (B) and the component (C) are used from the viewpoint of providing a lubricating oil composition having improved low temperature startability, shear stability, and cavitation suppressing effect in a well-balanced manner. The content ratio [(B) / (C)] is preferably 1/99 to 90/10, more preferably 5/85 to 80/20, and more preferably 10/90 to 70/30 in terms of mass ratio. , More preferably 15/85 to 60/40, even more preferably 20/80 to 50/50, and particularly preferably 25/75 to 45/55.
また、本発明の一態様の潤滑油組成物において、成分(B)及び成分(C)の合計含有量は、前記潤滑油組成物の全量(100質量%)基準で、低温始動性及びせん断安定性のバランスを良好とした潤滑油組成物とする観点から、好ましくは20.0質量%以下、より好ましくは16.0質量%以下、更に好ましくは10.0質量%以下、より更に好ましくは8.0質量%以下、特に好ましくは6.0質量%以下であり、また、キャビテーションの抑制効果をより向上させる観点から、好ましくは0.2質量%以上、より好ましくは0.6質量%以上、更に好ましくは1.0質量%以上、より更に好ましくは1.6質量%以上、特に好ましくは2.0質量%以上である。 Further, in the lubricating oil composition of one aspect of the present invention, the total content of the component (B) and the component (C) is based on the total amount (100% by mass) of the lubricating oil composition, and has low-temperature startability and shear stability. From the viewpoint of obtaining a lubricating oil composition having a good balance of properties, it is preferably 20.0% by mass or less, more preferably 16.0% by mass or less, still more preferably 10.0% by mass or less, still more preferably 8. It is 0.0% by mass or less, particularly preferably 6.0% by mass or less, and from the viewpoint of further improving the effect of suppressing cavitation, it is preferably 0.2% by mass or more, more preferably 0.6% by mass or more. It is more preferably 1.0% by mass or more, still more preferably 1.6% by mass or more, and particularly preferably 2.0% by mass or more.
なお、ハンドリング性や成分(A)との溶解性を考慮し、成分(B)及び(C)は、希釈油に溶解された溶液の形態で市販されていることが多い。
ただし、本明細書において、成分(B)及び(C)の含有量は、希釈油で希釈された溶液においては、希釈油の質量を除外した、成分(B)又は(C)を構成する樹脂分に換算した含有量である。
In consideration of handleability and solubility with the component (A), the components (B) and (C) are often marketed in the form of a solution dissolved in a diluted oil.
However, in the present specification, the content of the component (B) and (C) is the resin constituting the component (B) or (C) excluding the mass of the diluted oil in the solution diluted with the diluted oil. It is the content converted into minutes.
本発明の一態様の潤滑油組成物は、成分(B)~(C)以外の他の潤滑油用添加剤をさらに含有してもよい。
ただし、本発明の一態様の潤滑油組成物において、キャビテーションの抑制効果及び低温始動性をより向上させた潤滑油組成物とする観点から、成分(A)~(C)の合計含有量は、当該潤滑油組成物の全量(100質量%)基準で、好ましくは80~100質量%、より好ましくは85~100質量%、更に好ましくは90~100質量%、より更に好ましくは95~100質量%、特に好ましくは98~100質量%であり、さらに、98.5質量%超100質量%以下、99.0質量%超100質量%以下、99.5質量%超100質量%以下、又は99.7質量%超100質量%以下としてもよい。
The lubricating oil composition of one aspect of the present invention may further contain additives for lubricating oil other than the components (B) to (C).
However, in the lubricating oil composition of one aspect of the present invention, the total content of the components (A) to (C) is determined from the viewpoint of making the lubricating oil composition further improved in the effect of suppressing cavitation and the low temperature startability. Based on the total amount (100% by mass) of the lubricating oil composition, it is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass. Particularly preferably, it is 98 to 100% by mass, and more than 98.5% by mass and 100% by mass or less, 99.0% by mass and 100% by mass or less, 99.5% by mass and 100% by mass or less, or 99. It may be more than 7% by mass and 100% by mass or less.
以下、本発明の一態様の潤滑油組成物に含まれる各成分の詳細について説明する。 Hereinafter, details of each component contained in the lubricating oil composition of one aspect of the present invention will be described.
<成分(A):基油>
本発明の一態様で用いる成分(A)である基油としては、鉱油及び合成油から選ばれる1種以上が挙げられる。
鉱油としては、例えば、パラフィン系原油、中間基系原油、ナフテン系原油等の原油を常圧蒸留して得られる常圧残油;これらの常圧残油を減圧蒸留して得られる留出油;当該留出油を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、及び水素化精製等の精製処理を1つ以上施して得られる精製油;等が挙げられる。
<Ingredient (A): Base oil>
Examples of the base oil as the component (A) used in one embodiment of the present invention include one or more selected from mineral oils and synthetic oils.
Mineral oils include, for example, normal pressure residual oil obtained by atmospheric distillation of crude oils such as paraffin crude oil, intermediate base crude oil, and naphthenic crude oil; and distillate oil obtained by vacuum distillation of these normal pressure residual oils. ; Refined oil obtained by subjecting the distillate oil to one or more refining treatments such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining; and the like.
合成油としては、例えば、α-オレフィン単独重合体等のポリα-オレフィン;イソパラフィン;ポリアルキレングリコール;ポリオールエステル、二塩基酸エステル、リン酸エステル等のエステル系油;ポリフェニルエーテル等のエーテル系油;アルキルベンゼン;アルキルナフタレン;天然ガスからフィッシャー・トロプシュ法等により製造されるワックス(GTLワックス(Gas To Liquids WAX))を異性化することで得られる合成油(GTL)等が挙げられる。 Examples of the synthetic oil include polyα-olefins such as α-olefin homopolymers; isoparaffin; polyalkylene glycols; ester oils such as polyol esters, dibasic acid esters and phosphate esters; ether oils such as polyphenyl ethers. Oil; Alkylbenzene; Alkylnaphthalene; Synthetic oil (GTL) obtained by isomerizing a wax (GTL wax (Gas To Liquids WAX)) produced from natural gas by the Fischer-Tropsch method or the like can be mentioned.
これらの中でも、本発明の一態様で用いる成分(A)は、API(米国石油協会)基油カテゴリーのグループ2及びグループ3に分類される鉱油、並びに合成油から選ばれる1種以上を含むことが好ましい。 Among these, the component (A) used in one embodiment of the present invention includes mineral oils classified into Group 2 and Group 3 of the API (American Petroleum Institute) base oil category, and one or more selected from synthetic oils. Is preferable.
本発明の一態様で用いる成分(A)の40℃における動粘度は、好ましくは3.0~100mm2/s、より好ましくは4.0~70mm2/s、更に好ましくは5.0~40mm2/s、より更に好ましくは5.5~30mm2/s、特に好ましくは6.0~20mm2/sである。 The kinematic viscosity of the component (A) used in one aspect of the present invention at 40 ° C. is preferably 3.0 to 100 mm 2 / s, more preferably 4.0 to 70 mm 2 / s, still more preferably 5.0 to 40 mm. It is 2 / s, more preferably 5.5 to 30 mm 2 / s, and particularly preferably 6.0 to 20 mm 2 / s.
また、本発明の一態様で用いる成分(A)の粘度指数は、潤滑油組成物の用途に応じて適宜設定されるが、好ましくは70以上、より好ましくは80以上、更に好ましくは90以上、より更に好ましくは100以上、特に好ましくは105以上である。
なお、本発明の一態様において、成分(A)として、2種以上の基油を組み合わせた混合油を用いる場合、当該混合油の動粘度及び粘度指数が上記範囲であることが好ましい。
The viscosity index of the component (A) used in one aspect of the present invention is appropriately set according to the use of the lubricating oil composition, but is preferably 70 or more, more preferably 80 or more, still more preferably 90 or more. It is even more preferably 100 or more, and particularly preferably 105 or more.
In one aspect of the present invention, when a mixed oil in which two or more kinds of base oils are combined is used as the component (A), the kinematic viscosity and the viscosity index of the mixed oil are preferably in the above ranges.
本発明の一態様の潤滑油組成物において、成分(A)の含有量は、当該潤滑油組成物の全量(100質量%)基準で、好ましくは60質量%以上、より好ましくは70質量%以上、より好ましくは75質量%以上、更に好ましくは80質量%以上、より更に好ましくは85質量%以上、特に好ましくは90質量%以上であり、また、好ましくは99.8質量%以下、より好ましくは99.5質量%以下、更に好ましくは99.0質量%以下、より更に好ましくは98.5質量%以下、特に好ましくは98.0質量%以下である。 In the lubricating oil composition of one aspect of the present invention, the content of the component (A) is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total amount (100% by mass) of the lubricating oil composition. , More preferably 75% by mass or more, further preferably 80% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and preferably 99.8% by mass or less, more preferably. It is 99.5% by mass or less, more preferably 99.0% by mass or less, still more preferably 98.5% by mass or less, and particularly preferably 98.0% by mass or less.
<成分(B):ポリアルキル(メタ)アクリレート>
本発明の潤滑油組成物は、成分(B)として、重量平均分子量(Mw)が150,000~900,000のポリアルキル(メタ)アクリレートを含有する。Mwが150,000未満であるとキャビテーションの抑制効果が発現され難くなる。また、Mwが900,000より大きいとキャビテーション抑制効果とせん断安定性の両立が難しくなる傾向にある。なお、成分(B)と共に、後述の成分(C)を併用しているため、せん断安定性を良好とした潤滑油組成物に調整することができる。
<Component (B): Polyalkyl (meth) acrylate>
The lubricating oil composition of the present invention contains a polyalkyl (meth) acrylate having a weight average molecular weight (Mw) of 150,000 to 900,000 as the component (B). If Mw is less than 150,000, the effect of suppressing cavitation is less likely to be exhibited. Further, when Mw is larger than 900,000, it tends to be difficult to achieve both the cavitation suppressing effect and the shear stability. Since the component (C) described later is used in combination with the component (B), the lubricating oil composition can be adjusted to have good shear stability.
本発明の一態様で成分(B)として用いるポリアルキル(メタ)アクリレートの重量平均分子量(Mw)は、150,000以上であるが、キャビテーションの抑制効果及び低温始動性をより向上させた潤滑油組成物とする観点から、好ましくは200,000以上、より好ましくは250,000以上、より好ましくは260,000以上、より好ましくは270,000以上、より好ましくは300,000以上、更に好ましくは320,000以上、更に好ましくは350,000以上、更に好ましくは370,000以上、更に好ましくは400,000以上、より更に好ましくは420,000以上、より更に好ましくは450,000以上、より更に好ましくは470,000以上、より更に好ましくは500,000以上、特に好ましくは520,000以上であり、また、900,000以下であるが、せん断安定性をより良好とした潤滑油組成物とする観点から、好ましくは850,000以下、より好ましくは800,000以下、より好ましくは750,000以下、更に好ましくは700,000以下、より更に好ましくは650,000以下、特に好ましくは600,000以下である。 The weight average molecular weight (Mw) of the polyalkyl (meth) acrylate used as the component (B) in one aspect of the present invention is 150,000 or more, but the lubricating oil has further improved the effect of suppressing cavitation and the low temperature startability. From the viewpoint of the composition, it is preferably 200,000 or more, more preferably 250,000 or more, more preferably 260,000 or more, more preferably 270,000 or more, more preferably 300,000 or more, still more preferably 320. 000 or more, more preferably 350,000 or more, still more preferably 370,000 or more, still more preferably 400,000 or more, still more preferably 420,000 or more, still more preferably 450,000 or more, still more preferably. It is 470,000 or more, more preferably 500,000 or more, particularly preferably 520,000 or more, and 900,000 or less, but from the viewpoint of obtaining a lubricating oil composition having better shear stability. It is preferably 850,000 or less, more preferably 800,000 or less, more preferably 750,000 or less, still more preferably 700,000 or less, still more preferably 650,000 or less, and particularly preferably 600,000 or less. ..
本発明の一態様の潤滑油組成物において、成分(B)の含有量は、前記潤滑油組成物の全量(100質量%)基準で、キャビテーションの抑制効果及び低温始動性をより向上させた潤滑油組成物とする観点から、好ましくは0.1質量%以上、より好ましくは0.2質量%以上、更に好ましくは0.3質量%以上、より更に好ましくは0.5質量%以上、特に好ましくは0.7質量%以上であり、また、せん断安定性をより良好とした潤滑油組成物とする観点から、好ましくは10.0質量%以下、より好ましくは8.0質量%以下、更に好ましくは5.0質量%以下、より更に好ましくは3.0質量%以下、特に好ましくは2.0質量%以下である。 In the lubricating oil composition of one aspect of the present invention, the content of the component (B) is based on the total amount (100% by mass) of the lubricating oil composition, and the lubricating effect of suppressing cavitation and the low-temperature startability are further improved. From the viewpoint of making an oil composition, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably. Is 0.7% by mass or more, and is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, still more preferably, from the viewpoint of obtaining a lubricating oil composition having better shear stability. Is 5.0% by mass or less, more preferably 3.0% by mass or less, and particularly preferably 2.0% by mass or less.
本発明の一態様で用いる成分(B)は、アルキルアクリレート又はアルキルメタクリレート(以下、まとめて「アルキル(メタ)アクリレート」ともいう)に由来する構成単位を有する重合体であればよく、アルキル(メタ)アクリレート以外の他のモノマーに由来する構成単位を有する共重合体であってもよい。
当該アルキル(メタ)アクリレートが有するアルキル基の炭素数は、1以上、3以上、5以上、又は10以上としてもよく、また、60以下、40以下、30以下、又は20以下としてもよい。
The component (B) used in one embodiment of the present invention may be a polymer having a structural unit derived from an alkyl acrylate or an alkyl methacrylate (hereinafter collectively referred to as “alkyl (meth) acrylate”), and may be an alkyl (meth). ) It may be a copolymer having a structural unit derived from a monomer other than acrylate.
The number of carbon atoms of the alkyl group contained in the alkyl (meth) acrylate may be 1 or more, 3 or more, 5 or more, or 10 or more, and may be 60 or less, 40 or less, 30 or less, or 20 or less.
本発明の一態様で用いる成分(B)において、アルキル(メタ)アクリレートに由来する構成単位の含有量は、成分(B)の構成単位の全量(100モル%)基準で、10モル%以上、30モル%以上、50モル%以上、60モル%以上、70モル%以上、80モル%以上、90モル%以上、95モル%以上、又は99モル%以上としてもよい。 In the component (B) used in one embodiment of the present invention, the content of the structural unit derived from the alkyl (meth) acrylate is 10 mol% or more based on the total amount (100 mol%) of the structural unit of the component (B). It may be 30 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more.
≪櫛形ポリマー≫
本発明の一態様で用いる成分(B)は、櫛形ポリマーであってもよい。
本発明の一態様で成分(B)として用いる櫛形ポリマーとしては、高分子量の側鎖が出ている三叉分岐点を主鎖に数多くもつ構造を有する重合体であればよい。
≪Comb-shaped polymer≫
The component (B) used in one embodiment of the present invention may be a comb-shaped polymer.
The comb-shaped polymer used as the component (B) in one aspect of the present invention may be a polymer having a structure having a large number of three-pronged branch points in the main chain having high molecular weight side chains.
本発明の一態様で成分(B)として用いる櫛形ポリマーのSSI(せん断安定性指数)としては、好ましくは100以下、より好ましくは80以下、更に好ましくは70以下、より更に好ましくは60以下、特に好ましくは50以下である。
また、櫛形ポリマーのSSIは、下限値の制限は特に無いが、通常0.1以上である。
The SSI (shear stability index) of the comb polymer used as the component (B) in one aspect of the present invention is preferably 100 or less, more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, particularly. It is preferably 50 or less.
Further, the SSI of the comb polymer is not particularly limited to the lower limit value, but is usually 0.1 or more.
なお、本明細書において、SSI(せん断安定性指数)とは、重合体成分に由来するせん断による粘度低下をパーセンテージで示すものであり、JPI-5S-29-06に準拠して測定された値であって、より具体的には、下記計算式(1)より算出された値である。
・計算式(1):SSI(%)=(Kv0-Kv1)/(Kv0-Kvoil)×100
上記式(1)中、Kv0は、重合体成分を鉱油に希釈した試料油の100℃における動粘度の値であり、Kv1は、重合体成分を鉱油に希釈した試料油を、JPI-5S-29-06の手順にしたがって、出力法に準拠し、超音波を30分間照射した後の100℃における動粘度の値である。また、Kvoilは、重合体成分を希釈する際に用いた鉱油の100℃における動粘度の値である。
In the present specification, the SSI (shear stability index) indicates the decrease in viscosity due to shearing derived from the polymer component as a percentage, and is a value measured in accordance with JPI-5S-29-06. More specifically, it is a value calculated from the following formula (1).
-Calculation formula (1): SSI (%) = (Kv 0 -Kv 1 ) / (Kv 0 -Kv oil ) x 100
In the above formula (1), Kv 0 is the value of the kinematic viscosity of the sample oil obtained by diluting the polymer component with mineral oil at 100 ° C., and Kv 1 is the sample oil obtained by diluting the polymer component with mineral oil. It is the value of the kinematic viscosity at 100 ° C. after irradiation with ultrasonic waves for 30 minutes according to the output method according to the procedure of 5S-29-06. Further, Kv oil is a value of the kinematic viscosity of the mineral oil used for diluting the polymer component at 100 ° C.
なお、櫛形ポリマーのSSIの値は、その構造によって変化するものである。具体的には、以下に示す傾向があり、これらの事項を考慮することで、櫛形ポリマーのSSIの値は容易に調整できる。なお、以下の事項は、あくまで一例であって、これら以外の事項を考慮することによっても調整可能である。
・櫛形ポリマーの側鎖がマクロモノマー(x1)で構成され、当該マクロモノマー(x1)に由来する構成単位(X1)の含有量が、構成単位の全量(100モル%)基準で、0.5モル%以上である櫛形ポリマーは、SSIの値が低くなる傾向にある。
・櫛形ポリマーの側鎖を構成するマクロモノマー(x1)の分子量が大きくなるほど、SSIの値が低くなる傾向にある。
The SSI value of the comb polymer varies depending on its structure. Specifically, there is a tendency shown below, and the value of SSI of the comb-shaped polymer can be easily adjusted by considering these matters. The following items are just examples and can be adjusted by considering items other than these items.
-The side chain of the comb-shaped polymer is composed of a macromonomer (x1), and the content of the structural unit (X1) derived from the macromonomer (x1) is 0.5 based on the total amount (100 mol%) of the structural unit. Comb-shaped polymers of mol% or more tend to have lower SSI values.
-The larger the molecular weight of the macromonomer (x1) constituting the side chain of the comb-shaped polymer, the lower the SSI value tends to be.
本発明の一態様で成分(B)として用いる櫛形ポリマーは、マクロモノマー(x1)に由来する構成単位(X1)を少なくとも有する重合体が好ましい。この構成単位(X1)が、上述の「高分子量の側鎖」に該当する。
なお、本明細書において、上記の「マクロモノマー(x1)」とは、重合性官能基を有する高分子量モノマーのことを意味し、末端に重合性官能基を有する高分子量モノマーであることが好ましい。
The comb-shaped polymer used as the component (B) in one aspect of the present invention is preferably a polymer having at least a structural unit (X1) derived from the macromonomer (x1). This structural unit (X1) corresponds to the above-mentioned "high molecular weight side chain".
In the present specification, the above-mentioned "macromonomer (x1)" means a high molecular weight monomer having a polymerizable functional group, and is preferably a high molecular weight monomer having a polymerizable functional group at the terminal. ..
本発明の一態様で成分(B)として用いる櫛形ポリマーにおいて、構成単位(X1)の含有量は、当該櫛形ポリマーの構成単位の全量(100モル%)基準で、好ましくは0.5~20モル%、より好ましくは0.7~10モル%、更に好ましくは0.9~5モル%である。
なお、本明細書において、櫛形ポリマーの構成単位の含有量は、13C-NMR定量スペクトルを解析して算出した値を意味する。
In the comb polymer used as the component (B) in one aspect of the present invention, the content of the constituent unit (X1) is preferably 0.5 to 20 mol based on the total amount (100 mol%) of the constituent units of the comb polymer. %, More preferably 0.7 to 10 mol%, still more preferably 0.9 to 5 mol%.
In the present specification, the content of the constituent unit of the comb-shaped polymer means a value calculated by analyzing the 13 C-NMR quantitative spectrum.
マクロモノマー(x1)の数平均分子量(Mn)としては、好ましくは300以上、より好ましくは400以上、更に好ましくは500以上であり、また、好ましくは100,000以下、より好ましくは50,000以下、更に好ましくは20,000以下である。
つまり、マクロモノマー(x1)の数平均分子量(Mn)は、好ましくは300~100,000、より好ましくは400~50,000、更に好ましくは500~20,000である。
The number average molecular weight (Mn) of the macromonomer (x1) is preferably 300 or more, more preferably 400 or more, still more preferably 500 or more, and preferably 100,000 or less, more preferably 50,000 or less. , More preferably 20,000 or less.
That is, the number average molecular weight (Mn) of the macromonomer (x1) is preferably 300 to 100,000, more preferably 400 to 50,000, and even more preferably 500 to 20,000.
マクロモノマー(x1)が有する重合性官能基としては、例えば、アクリロイル基(CH2=CH-COO-)、メタクリロイル基(CH2=CCH3-COO-)、エテニル基(CH2=CH-)、ビニルエーテル基(CH2=CH-O-)、アリル基(CH2=CH-CH2-)、アリルエーテル基(CH2=CH-CH2-O-)、CH2=CH-CONH-で表される基、CH2=CCH3-CONH-で表される基等が挙げられる。 Examples of the polymerizable functional group of the macromonomer (x1) include an acryloyl group (CH 2 = CH-COO-), a methacryloyl group (CH 2 = CCH 3 -COO-), and an ethenyl group (CH 2 = CH-). , Vinyl ether group (CH 2 = CH-O-), allyl group (CH 2 = CH-CH 2- ), allyl ether group (CH 2 = CH-CH 2 -O-), CH 2 = CH-CONH- Examples thereof include a group represented by CH2 = CCH3-CONH-.
マクロモノマー(x1)は、上記重合性官能基以外に、例えば、以下の一般式(i)~(iii)で表される繰り返し単位を1種以上有していてもよい。
上記一般式(i)中、Rb1は、炭素数1~10の直鎖又は分岐鎖のアルキレン基である。
上記一般式(ii)中、Rb2は、炭素数2~4の直鎖又は分岐鎖のアルキレン基である。
上記一般式(iii)中、Rb3は、水素原子又はメチル基である。Rb4は、炭素数1~10の直鎖又は分岐鎖のアルキル基である。
なお、上記一般式(i)~(iii)で表される繰り返し単位をそれぞれ複数有する場合には、複数のRb1、Rb2、Rb3、及びRb4は、それぞれ同一であってもよく、互いに異なるものであってもよい。
In the above general formula (i), R b1 is a linear or branched alkylene group having 1 to 10 carbon atoms.
In the above general formula (ii), R b2 is a linear or branched alkylene group having 2 to 4 carbon atoms.
In the above general formula (iii), R b3 is a hydrogen atom or a methyl group. R b4 is a linear or branched alkyl group having 1 to 10 carbon atoms.
When each of the plurality of repeating units represented by the above general formulas (i) to (iii) is provided, the plurality of R b1 , R b2 , R b3 , and R b4 may be the same. They may be different from each other.
本発明の一態様において、マクロモノマー(x1)は、前記一般式(i)で表される繰り返し単位を有する重合体であることが好ましく、前記一般式(i)中のRb1が1,2-ブチレン基及び1,4-ブチレン基の少なくとも一方である繰り返し単位(X1-1)を有する重合体であることがより好ましい。 In one aspect of the present invention, the macromonomer (x1) is preferably a polymer having a repeating unit represented by the general formula (i), and R b1 in the general formula (i) is 1,2. -A polymer having a repeating unit (X1-1) which is at least one of a butylene group and a 1,4-butylene group is more preferable.
繰り返し単位(X1-1)の含有量としては、マクロモノマー(x1)の構成単位の全量(100モル%)基準で、好ましくは1~100モル%、より好ましくは20~95モル%、更に好ましくは40~90モル%、より更に好ましくは50~80モル%である。 The content of the repeating unit (X1-1) is preferably 1 to 100 mol%, more preferably 20 to 95 mol%, still more preferably, based on the total amount (100 mol%) of the constituent units of the macromonomer (x1). Is 40 to 90 mol%, more preferably 50 to 80 mol%.
なお、マクロモノマー(x1)が、前記一般式(i)~(iii)から選ばれる2種以上の繰り返し単位を有する共重合体である場合、共重合の形態としては、ブロック共重合体であってもよく、ランダム共重合体であってもよい。 When the macromonomer (x1) is a copolymer having two or more repeating units selected from the general formulas (i) to (iii), the form of copolymerization is a block copolymer. It may be a random copolymer or a random copolymer.
本発明の一態様で成分(B)として用いる櫛形ポリマーは、1種類のマクロモノマー(x1)に由来する構成単位(X1)のみからなる単独重合体でもよく、2種類以上のマクロモノマー(x1)に由来する構成単位(X1)を有する共重合体であってもよい。
また、本発明の一態様で成分(B)として用いる櫛形ポリマーは、マクロモノマー(x1)に由来する構成単位(X1)と共に、マクロモノマー(x1)以外の他のモノマーに由来する構成単位(X2)を有する共重合体であってもよい。
このような櫛形ポリマーの具体的な構造としては、モノマー(x2)に由来する構成単位(X2)を含む主鎖に対して、マクロモノマー(x1)に由来する構成単位(X1)を含む側鎖を有する共重合体が好ましい。
The comb-shaped polymer used as the component (B) in one aspect of the present invention may be a homopolymer consisting of only a structural unit (X1) derived from one type of macromonomer (x1), or two or more types of macromonomers (x1). It may be a copolymer having a structural unit (X1) derived from.
Further, the comb-shaped polymer used as the component (B) in one aspect of the present invention has a structural unit (X1) derived from the macromonomer (x1) and a structural unit (X2) derived from a monomer other than the macromonomer (x1). ) May be a copolymer.
As a specific structure of such a comb-shaped polymer, a main chain containing a structural unit (X2) derived from a monomer (x2) is opposed to a side chain containing a structural unit (X1) derived from a macromonomer (x1). A copolymer having the above is preferable.
モノマー(x2)としては、例えば、アルキル(メタ)アクリレート、窒素原子含有ビニル単量体、水酸基含有ビニル単量体、リン原子含有単量体、脂肪族炭化水素系ビニル単量体、脂環式炭化水素系ビニル単量体、ビニルエステル類、ビニルエーテル類、ビニルケトン類、エポキシ基含有ビニル単量体、ハロゲン元素含有ビニル単量体、不飽和ポリカルボン酸のエステル、(ジ)アルキルフマレート、(ジ)アルキルマレエート、芳香族炭化水素系ビニル単量体等が挙げられる。 Examples of the monomer (x2) include an alkyl (meth) acrylate, a nitrogen atom-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, a phosphorus atom-containing monomer, an aliphatic hydrocarbon-based vinyl monomer, and an alicyclic type. Hydrocarbon-based vinyl monomers, vinyl esters, vinyl ethers, vinyl ketones, epoxy group-containing vinyl monomers, halogen element-containing vinyl monomers, unsaturated polycarboxylic acid esters, (di) alkyl fumarate, ( D) Alkyl maleate, aromatic hydrocarbon-based vinyl monomer and the like can be mentioned.
なお、モノマー(x2)としては、リン原子含有単量体及び芳香族炭化水素系ビニル単量体以外の単量体が好ましく、下記一般式(a1)で表される単量体、アルキル(メタ)アクリレート、及び水酸基含有ビニル単量体から選ばれる1種以上を含むことがより好ましく、水酸基含有ビニル単量体(x2-d)を少なくとも含むことが更に好ましい。
上記一般式(a1)中、Rb11は、水素原子又はメチル基である。
Rb12は、単結合、炭素数1~10の直鎖又は分岐鎖のアルキレン基、-O-、又は-NH-である。
Rb13は、炭素数2~4の直鎖又は分岐鎖のアルキレン基である。また、nは1以上の整数(好ましくは1~20の整数、より好ましくは1~5の整数)を示す。なお、nが2以上の整数の場合、複数のRb13は、同一であってもよく、異なっていてもよく、さらに、(Rb13O)n部分は、ランダム結合でもブロック結合でもよい。
Rb14は、炭素数1~60(好ましくは10~50、より好ましくは20~40)の直鎖又は分岐鎖のアルキル基である。
In the above general formula (a1), R b11 is a hydrogen atom or a methyl group.
R b12 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, -O-, or -NH-.
R b13 is a linear or branched alkylene group having 2 to 4 carbon atoms. Further, n represents an integer of 1 or more (preferably an integer of 1 to 20, more preferably an integer of 1 to 5). When n is an integer of 2 or more, the plurality of R b13s may be the same or different, and the (R b13 O) n portion may be a random bond or a block bond.
R b14 is a linear or branched alkyl group having 1 to 60 carbon atoms (preferably 10 to 50, more preferably 20 to 40).
<オレフィン共重合体(C)>
本発明の潤滑油組成物は、成分(C)として、重量平均分子量(Mw)が100,000以下のオレフィン共重合体を含有する。Mwが当該範囲のオレフィン共重合体を成分(B)と併用することで、キャビテーションの抑制効果及びせん断安定性を向上させた潤滑油組成物とすることができる。なお、成分(C)と共に、前述の成分(B)を併用しているため、低温始動性を良好とした潤滑油組成物に調整することができる。
<Olefin copolymer (C)>
The lubricating oil composition of the present invention contains an olefin copolymer having a weight average molecular weight (Mw) of 100,000 or less as the component (C). By using the olefin copolymer in the range of Mw in combination with the component (B), a lubricating oil composition having an improved cavitation suppressing effect and shear stability can be obtained. Since the above-mentioned component (B) is used in combination with the component (C), the lubricating oil composition can be adjusted to have good low-temperature startability.
本発明の一態様で成分(C)として用いるオレフィン共重合体の重量平均分子量(Mw)は、100,000以下であるが、キャビテーションの抑制効果をより向上させつつ、低温始動性及びせん断安定性をより良好とした潤滑油組成物とする観点から、好ましくは80,000以下、より好ましくは70,000以下、より好ましくは60,000以下、更に好ましくは40,000以下、より更に好ましくは30,000以下、特に好ましくは25,000以下である。
また、成分(C)であるオレフィン共重合体の重量平均分子量(Mw)は、500以上、1,000以上、3,000以上、5,000以上、7,000以上、8,000以上、8,000超、8,500以上、9,000以上、9,500以上、10,000以上、11,000以上、12,000以上、又は13,000以上としてもよい。
The weight average molecular weight (Mw) of the olefin copolymer used as the component (C) in one aspect of the present invention is 100,000 or less, but the low temperature startability and shear stability are improved while further improving the effect of suppressing cavitation. From the viewpoint of obtaining a better lubricating oil composition, preferably 80,000 or less, more preferably 70,000 or less, more preferably 60,000 or less, still more preferably 40,000 or less, still more preferably 30. It is 000 or less, particularly preferably 25,000 or less.
The weight average molecular weight (Mw) of the olefin copolymer as the component (C) is 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 7,000 or more, 8,000 or more, 8. It may be over 000, 8,000 or more, 9,000 or more, 9,500 or more, 10,000 or more, 11,000 or more, 12,000 or more, or 13,000 or more.
本発明の一態様の潤滑油組成物において、成分(C)の含有量は、前記潤滑油組成物の全量(100質量%)基準で、キャビテーションの抑制効果及びせん断安定性をより向上させた潤滑油組成物とする観点から、好ましくは0.1質量%以上、より好ましくは0.3質量%以上、更に好ましくは0.5質量%以上、より更に好ましくは0.8質量%以上、特に好ましくは1.0質量%以上であり、また、低温始動性をより良好とした潤滑油組成物とする観点から、好ましくは10.0質量%以下、より好ましくは8.0質量%以下、更に好ましくは5.0質量%以下、より更に好ましくは4.0質量%以下、特に好ましくは3.0質量%以下であり、さらに、2.5質量%以下、又は2.0質量%以下としてもよい。 In the lubricating oil composition of one aspect of the present invention, the content of the component (C) is based on the total amount (100% by mass) of the lubricating oil composition, and the effect of suppressing cavitation and the shear stability are further improved. From the viewpoint of making an oil composition, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and particularly preferably. Is 1.0% by mass or more, and is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, still more preferably, from the viewpoint of obtaining a lubricating oil composition having better low-temperature startability. Is 5.0% by mass or less, more preferably 4.0% by mass or less, particularly preferably 3.0% by mass or less, and further, 2.5% by mass or less, or 2.0% by mass or less. ..
本発明の一態様で用いる成分(C)としては、アルケニル基を有するモノマーに由来の構成単位を有する共重合体であって、例えば、炭素数2~20(好ましくは2~16、より好ましくは2~14)のα-オレフィンの共重合体が挙げられ、より具体的には、エチレン-α-オレフィン共重合体が好ましい。
なお、エチレン-α-オレフィン共重合体を構成するα-オレフィンの炭素数としては、好ましくは3~20であるが、より好ましくは3~16、更に好ましくは3~14、より更に好ましくは3~6、特に好ましくは3である。
The component (C) used in one embodiment of the present invention is a copolymer having a structural unit derived from a monomer having an alkenyl group, and is, for example, a copolymer having 2 to 20 carbon atoms (preferably 2 to 16 carbon atoms, more preferably 2 to 16 carbon atoms). Examples thereof include the α-olefin copolymers of 2 to 14), and more specifically, the ethylene-α-olefin copolymer is preferable.
The number of carbon atoms of the α-olefin constituting the ethylene-α-olefin copolymer is preferably 3 to 20, more preferably 3 to 16, still more preferably 3 to 14, and even more preferably 3. ~ 6, particularly preferably 3.
なお、本発明の一態様で用いる成分(C)は、分散型オレフィン系共重合体であってもよい。
分散型オレフィン系共重合体としては、上述のエチレン-α-オレフィン共重合体に対して、マレイン酸、N-ビニルピロリドン、N-ビニルイミダゾール、グリシジルアクリレート等をグラフト重合してなる共重合体が挙げられる。
The component (C) used in one aspect of the present invention may be a dispersed olefin-based copolymer.
As the dispersed olefin-based copolymer, a copolymer obtained by graft-polymerizing the above-mentioned ethylene-α-olefin copolymer with maleic acid, N-vinylpyrrolidone, N-vinylimidazole, glycidyl acrylate and the like. Can be mentioned.
また、本発明の一態様で用いる成分(C)は、アルケニル基を有するモノマーに由来の構成単位と共に、さらに芳香族モノマーに由来の構成単位を有する共重合体であってもよい。このようなオレフィン系共重合体としては、例えば、スチレン-ジエン共重合体、スチレン-イソプレン共重合体等のスチレン系共重合体が挙げられる。 Further, the component (C) used in one embodiment of the present invention may be a copolymer having a structural unit derived from a monomer having an alkenyl group and further having a structural unit derived from an aromatic monomer. Examples of such an olefin-based copolymer include styrene-based copolymers such as a styrene-diene copolymer and a styrene-isoprene copolymer.
これらの中でも、キャビテーションの抑制効果及びせん断安定性を向上させた潤滑油組成物とする観点から、本発明の一態様で用いる成分(C)は、エチレンプロピレン共重合体(C1)を含むことが好ましい。
本発明の一態様の潤滑油組成物において、成分(C1)の含有割合は、当該潤滑油組成物に含まれる成分(C)の全量(100質量%)に対して、好ましくは30~100質量%、より好ましくは50~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、特に好ましくは90~100質量%である。
Among these, the component (C) used in one aspect of the present invention may contain an ethylene propylene copolymer (C1) from the viewpoint of obtaining a lubricating oil composition having an effect of suppressing cavitation and improved shear stability. preferable.
In the lubricating oil composition of one aspect of the present invention, the content ratio of the component (C1) is preferably 30 to 100% by mass with respect to the total amount (100% by mass) of the component (C) contained in the lubricating oil composition. %, More preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.
<潤滑油用添加剤>
本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、必要に応じて、成分(B)及び成分(C)以外の潤滑油用添加剤をさらに含有してもよい。
このような潤滑油用添加剤としては、例えば、フェノール系酸化防止剤、アミノ系酸化防止剤等の酸化防止剤;金属スルホネート、金属サリシレート、金属フェネート等の金属系清浄剤;アルケニルコハク酸イミド等の無灰系分散剤;モリブデン系摩擦調整剤、脂肪酸エステル、脂肪酸、脂肪族アルコール等の摩擦調整剤;ジチオリン酸亜鉛等の耐摩耗剤;リン系極圧剤、硫黄系極圧剤、硫黄-リン系極圧剤等の極圧剤;シリコーン系消泡剤等の消泡剤;ベンゾトリアゾール系化合物等の金属不活性化剤;防錆剤;帯電防止剤;等が挙げられる。
これらの潤滑油用添加剤は、それぞれ、単独で用いてもよく、2種以上を併用してもよい。
<Additives for lubricating oil>
The lubricating oil composition of one aspect of the present invention may further contain an additive for lubricating oil other than the component (B) and the component (C), if necessary, as long as the effect of the present invention is not impaired. ..
Examples of such additives for lubricating oil include antioxidants such as phenol-based antioxidants and amino-based antioxidants; metal-based detergents such as metal sulfonates, metal salicylates, and metal phenates; alkenyl succinate imide and the like. Ash-free dispersant; Molybdenum-based friction modifier, fatty acid ester, fatty acid, friction modifier such as aliphatic alcohol; Abrasion resistant agent such as zinc dithiophosphate; Phosphorus-based extreme pressure agent, sulfur-based extreme pressure agent, sulfur- Extreme pressure agents such as phosphorus-based extreme pressure agents; defoaming agents such as silicone-based defoaming agents; metal inactivating agents such as benzotriazole-based compounds; rust preventives; antistatic agents; and the like.
These lubricant additives may be used alone or in combination of two or more.
これらの潤滑油用添加剤のそれぞれの含有量は、本発明の効果を損なわない範囲内で、適宜調製することができるが、潤滑油組成物の全量(100質量%)基準で、それぞれの添加剤ごとに独立して、通常0.001~15質量%、好ましくは0.005~10質量%、より好ましくは0.01~5質量%である。 The content of each of these additives for lubricating oil can be appropriately prepared within a range that does not impair the effects of the present invention, but each addition is based on the total amount (100% by mass) of the lubricating oil composition. Independently for each agent, it is usually 0.001 to 15% by mass, preferably 0.005 to 10% by mass, and more preferably 0.01 to 5% by mass.
<潤滑油組成物の製造方法>
本発明の一態様の潤滑油組成物の製造方法としては、特に制限はないが、生産性の観点から、成分(A)に、成分(B)及び成分(C)、並びに、必要に応じて、他の潤滑油用添加剤を配合する工程を有する、方法であることが好ましい。
なお、成分(B)及び成分(C)等の樹脂成分は、成分(A)との相溶性の観点から、希釈油に溶解された溶液の形態とし、当該溶液を成分(A)に配合することが好ましい。
<Manufacturing method of lubricating oil composition>
The method for producing the lubricating oil composition according to one aspect of the present invention is not particularly limited, but from the viewpoint of productivity, the component (A) includes the component (B) and the component (C), and if necessary. , It is preferable that the method has a step of blending other additives for lubricating oil.
The resin components such as the component (B) and the component (C) are in the form of a solution dissolved in the diluted oil from the viewpoint of compatibility with the component (A), and the solution is blended with the component (A). Is preferable.
〔潤滑油組成物の性状〕
本発明の一態様の潤滑油組成物の40℃における動粘度は、好ましくは5.0~130mm2/s、より好ましくは6.5~100mm2/s、更に好ましくは8.0~100mm2/s、より更に好ましくは10.0~60mm2/s、特に好ましくは11.0~40mm2/sである。
[Characteristics of lubricating oil composition]
The kinematic viscosity of the lubricating oil composition of one aspect of the present invention at 40 ° C. is preferably 5.0 to 130 mm 2 / s, more preferably 6.5 to 100 mm 2 / s, still more preferably 8.0 to 100 mm 2 . / S, more preferably 10.0 to 60 mm 2 / s, and particularly preferably 11.0 to 40 mm 2 / s.
本発明の一態様の潤滑油組成物の100℃における動粘度は、好ましくは2.0~30mm2/s、より好ましくは2.3~20mm2/s、更に好ましくは2.6~15mm2/s、より更に好ましくは3.0~10mm2/s、特に好ましくは3.2~7.0mm2/sである。 The kinematic viscosity of the lubricating oil composition of one aspect of the present invention at 100 ° C. is preferably 2.0 to 30 mm 2 / s, more preferably 2.3 to 20 mm 2 / s, still more preferably 2.6 to 15 mm 2 . / S, more preferably 3.0 to 10 mm 2 / s, and particularly preferably 3.2 to 7.0 mm 2 / s.
本発明の一態様の潤滑油組成物の150℃における動粘度は、好ましくは1.0~20mm2/s、より好ましくは1.2~10mm2/s、更に好ましくは1.4~7.0mm2/s、より更に好ましくは1.6~5.0mm2/s、特に好ましくは1.8~3.0mm2/sである。 The kinematic viscosity of the lubricating oil composition of one aspect of the present invention at 150 ° C. is preferably 1.0 to 20 mm 2 / s, more preferably 1.2 to 10 mm 2 / s, and even more preferably 1.4 to 7. It is 0 mm 2 / s, more preferably 1.6 to 5.0 mm 2 / s, and particularly preferably 1.8 to 3.0 mm 2 / s.
本発明の一態様の潤滑油組成物の粘度指数は、好ましくは100以上、より好ましくは120以上、更に好ましくは140以上、より更に好ましくは160以上、特に好ましくは180以上である。 The viscosity index of the lubricating oil composition according to one aspect of the present invention is preferably 100 or more, more preferably 120 or more, still more preferably 140 or more, still more preferably 160 or more, and particularly preferably 180 or more.
本発明の一態様の潤滑油組成物の-40℃におけるBF粘度(ブルックフィールド粘度)は、低温始動性が良好な潤滑油組成物とする観点から、好ましくは1500mPa・s以下、より好ましくは1400mPa・s以下、更に好ましくは1300mPa・s以下、より更に好ましくは1200mPa・s以下であり、また、好ましくは100mPa・s以上、より好ましくは300mPa・s以上、更に好ましくは500mPa・s以上、より更に好ましくは700mPa・s以上である。
なお、本明細書において、BF粘度は、ASTM D2983-09に準拠して測定した値を意味する。
The BF viscosity (Brookfield viscosity) of the lubricating oil composition according to one aspect of the present invention at −40 ° C. is preferably 1500 mPa · s or less, more preferably 1400 mPa, from the viewpoint of obtaining a lubricating oil composition having good low-temperature startability. -S or less, more preferably 1300 mPa · s or less, still more preferably 1200 mPa · s or less, preferably 100 mPa · s or more, more preferably 300 mPa · s or more, still more preferably 500 mPa · s or more, still more. It is preferably 700 mPa · s or more.
In this specification, the BF viscosity means a value measured according to ASTM D2983-09.
本発明の一態様の潤滑油組成物の後述の実施例に記載の方法に準拠して算出された動粘度低下率は、せん断安定性が良好な潤滑油組成物とする観点から、好ましくは11.0%未満、より好ましくは10.5%未満、更に好ましくは10.0%未満、より更に好ましくは9.5%未満である。 The rate of decrease in kinematic viscosity calculated according to the method described in Examples described later for the lubricating oil composition of one aspect of the present invention is preferably 11 from the viewpoint of obtaining a lubricating oil composition having good shear stability. It is less than 0.0%, more preferably less than 10.5%, even more preferably less than 10.0%, still more preferably less than 9.5%.
本発明の一態様の潤滑油組成物の後述の実施例に記載の方法に準拠して算出されたキャビテーション係数の値は、キャビテーションの抑制効果に優れた潤滑油組成物とする観点から、好ましくは0.45以下、より好ましくは0.44以下、更に好ましくは0.43以下であり、また、通常は0.40以上である。 The value of the cavitation coefficient calculated according to the method described in Examples described later for the lubricating oil composition of one aspect of the present invention is preferably from the viewpoint of obtaining a lubricating oil composition having an excellent effect of suppressing cavitation. It is 0.45 or less, more preferably 0.44 or less, still more preferably 0.43 or less, and usually 0.40 or more.
〔潤滑油組成物の特性、用途〕
本発明の一態様の潤滑油組成物は、低温始動性、せん断安定性、及びキャビテーションの抑制効果等の優れた特性を有する。
そのため、本発明の一態様の潤滑油組成物は、緩衝器の潤滑に好適に使用し得、より具体的には、複筒型ショックアブソーバー及び単筒型ショックアブソーバーの何れにも使用可能であり、二輪用及び四輪用のいずれのショックアブソーバーにも好適に使用し得る。
本発明の一態様の潤滑油組成物のこれらの特性を考慮すると、本発明は、以下の[1]及び[2]も提供し得る。
[1]上述の本発明の一態様の潤滑油組成物を充填した、緩衝器。
[2]上述の本発明の一態様の潤滑油組成物を緩衝器の潤滑に適用する、潤滑油組成物の使用。
[Characteristics and applications of lubricating oil composition]
The lubricating oil composition of one aspect of the present invention has excellent properties such as low temperature startability, shear stability, and cavitation suppressing effect.
Therefore, the lubricating oil composition according to one aspect of the present invention can be suitably used for lubricating a shock absorber, and more specifically, it can be used for both a double-cylinder shock absorber and a single-cylinder shock absorber. , Can be suitably used for both two-wheeled and four-wheeled shock absorbers.
Considering these properties of the lubricating oil composition of one aspect of the present invention, the present invention may also provide the following [1] and [2].
[1] A shock absorber filled with the above-mentioned lubricating oil composition according to one aspect of the present invention.
[2] Use of a lubricating oil composition, which applies the above-mentioned lubricating oil composition of one aspect of the present invention to lubricate a shock absorber.
次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。なお、各種物性の測定法は、下記のとおりである。 Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The methods for measuring various physical properties are as follows.
(1)動粘度、粘度指数
JIS K2283:2000に準拠して測定及び算出した。
(2)重量平均分子量(Mw)
ゲル浸透クロマトグラフ装置(アジレント社製、「1260型HPLC」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(測定条件)
・カラム:「Shodex LF404」を2本、順次連結したもの。
・カラム温度:35℃
・展開溶媒:クロロホルム
・流速:0.3mL/min
(1) Kinematic viscosity, viscosity index Measured and calculated according to JIS K2283: 2000.
(2) Weight average molecular weight (Mw)
It was measured under the following conditions using a gel permeation chromatograph device (manufactured by Agilent, "1260 type HPLC"), and the value measured in terms of standard polystyrene was used.
(Measurement condition)
-Column: Two "Shodex LF404" are connected in sequence.
-Column temperature: 35 ° C
・ Developing solvent: Chloroform ・ Flow rate: 0.3 mL / min
実施例1、比較例1~8
表1に示す種類及び配合量にて、基油に、各種添加剤を配合し、潤滑油組成物をそれぞれ調製した。なお、表1に記載された各種添加剤の配合量は、希釈油で溶解された状態で配合したとしても、当該希釈油の質量を除いた有効成分換算(固形分換算)での配合量を記載している。
また、それぞれの潤滑油組成物の調製に使用した、基油及び各種添加剤の詳細は以下のとおりである。
Example 1, Comparative Examples 1 to 8
Various additives were blended with the base oil according to the types and blending amounts shown in Table 1, and lubricating oil compositions were prepared respectively. The blending amounts of the various additives shown in Table 1 are the blending amounts in terms of active ingredients (solid content equivalent) excluding the mass of the diluted oil, even if they are blended in a state of being dissolved in the diluted oil. It is described.
The details of the base oil and various additives used for preparing each lubricating oil composition are as follows.
<基油>
・「パラフィン系鉱油」:40℃動粘度=7.1mm2/s、100℃動粘度=2.17mm2/s、粘度指数=109、15℃密度=0.82g/cm3である、パラフィン系鉱油。
<PMA>
・「PMA(55万)」:重量平均分子量(Mw)=55万のポリアルキル(メタ)アクリレート。
・「PMA(2.9万)」:重量平均分子量(Mw)=2.9万のポリアルキル(メタ)アクリレート。
・「PMA(14万)」:重量平均分子量(Mw)=14万のポリアルキル(メタ)アクリレート。
<OCP>
・「OCP(1.7万)」:重量平均分子量(Mw)=1.7万のエチレンプロピレン共重合体。
・「OCP(78万)」:重量平均分子量(Mw)=78万のオレフィン共重合体。
<Base oil>
"Paraffin-based mineral oil": 40 ° C. kinematic viscosity = 7.1 mm 2 / s, 100 ° C. kinematic viscosity = 2.17 mm 2 / s, viscosity index = 109, 15 ° C. density = 0.82 g / cm 3 , paraffin System mineral oil.
<PMA>
"PMA (550,000)": Polyalkyl (meth) acrylate having a weight average molecular weight (Mw) = 550,000.
"PMA (29,000)": Polyalkyl (meth) acrylate having a weight average molecular weight (Mw) of 29,000.
"PMA (140,000)": Polyalkyl (meth) acrylate having a weight average molecular weight (Mw) = 140,000.
<OCP>
"OCP (17,000)": Ethylene propylene copolymer having a weight average molecular weight (Mw) of 17,000.
"OCP (780,000)": An olefin copolymer having a weight average molecular weight (Mw) = 780,000.
調製した潤滑油組成物について、上述の方法に準拠して、40℃動粘度、100℃動粘度、150℃動粘度、及び粘度指数を測定又は算出すると共に、以下の測定又は評価を行った。これらの結果を表1に示す。 The prepared lubricating oil composition was measured or calculated for 40 ° C. kinematic viscosity, 100 ° C. kinematic viscosity, 150 ° C. kinematic viscosity, and viscosity index, and the following measurements or evaluations were performed. These results are shown in Table 1.
(1)低温始動性の評価
ASTM D2983-09に準拠して、-40℃におけるBF粘度を測定した。
当該BF粘度が低いほど、低温始動性に優れた潤滑油組成物であるといえ、-40℃におけるBF粘度が1500mPa・s以下である場合、低温始動性に優れた潤滑油組成物と判断した。
(1) Evaluation of low temperature startability The BF viscosity at −40 ° C. was measured according to ASTM D2983-09.
It can be said that the lower the BF viscosity is, the more excellent the low temperature startability is, and when the BF viscosity at −40 ° C. is 1500 mPa · s or less, it is determined that the lubricating oil composition is excellent in low temperature startability. ..
(2)せん断安定性の評価
せん断試験は、超音波A法(JPI-5S-29)に準拠し、調製した潤滑油組成物を試料油とし、当該試料油30mLに、25℃で、超音波を60分間照射した。なお、超音波の出力電圧は、予め40℃動粘度を測定した標準油30mLに、25℃で、超音波を60分間照射した後の40℃動粘度の低下率が25%となる出力電圧の値を採用した。
そして、せん断試験前後での試料油の40℃動粘度を測定し、下記式から動粘度低下率を算出し、せん断安定性を評価した。
・動粘度低下率(%)=([せん断試験前の試料油の40℃動粘度]-[せん断試験後の試料油の40℃動粘度])/[せん断試験前の試料油の40℃動粘度]×100
当該動粘度低下率の値が小さいほど、せん断安定性に優れた潤滑油組成物であるといえ、動粘度低下率の値が11.0%未満である場合、せん断安定性に優れた潤滑油組成物と判断した。
(2) Evaluation of shear stability The shear test is based on the ultrasonic A method (JPI-5S-29), and the prepared lubricating oil composition is used as the sample oil, and ultrasonic waves are applied to 30 mL of the sample oil at 25 ° C. Was irradiated for 60 minutes. The output voltage of the ultrasonic wave is 30 mL of standard oil whose kinematic viscosity has been measured in advance at 40 ° C., and the output voltage has a decrease rate of 40 ° C. Adopted the value.
Then, the kinematic viscosity of the sample oil at 40 ° C. before and after the shear test was measured, the rate of decrease in kinematic viscosity was calculated from the following formula, and the shear stability was evaluated.
-Decrease rate of kinematic viscosity (%) = ([40 ° C kinematic viscosity of sample oil before shear test]-[40 ° C kinematic viscosity of sample oil after shear test]) / [40 ° C dynamic of sample oil before shear test] Viscosity] x 100
It can be said that the smaller the value of the kinematic viscosity reduction rate is, the more excellent the shear stability is, and when the value of the kinematic viscosity reduction rate is less than 11.0%, the lubricating oil is excellent in shear stability. It was judged to be a composition.
(3)キャビテーションの抑制効果の評価
図1は、キャビテーションの抑制効果を評価するための試験装置の模式図である。図1に示す試験装置1は、評価対象の試料油を貯めるオイルタンク11、試料油を循環させるポンプ12、試料油の温度を調整するヒータ13、試料油の流速を管理する流量計14、試料油の流れを制御するバルブ15a、15b、15c、側面にサファイア製の観察窓を備え、上流側の入口に直径1mmのオリフィス16aを備える観察タンク16、観察タンクの上流側と下流側にそれぞれ圧力計17a、17b、及び熱電対18を有する。
初めに、調製した潤滑油組成物を試料油としてオイルタンク11に充填し、バルブ15a、15b、15cを全開とし、ポンプ12及びヒータ13を作動して、流路1及び流路2に沿って、試料油を循環させながら、観察タンク16にも試料油を充填した。そして、試料油の温度が150℃に達して安定化した状態を初期状態とした。
初期状態から、バルブ15cを全開の状態から徐々に閉めて、試料油の流路2に沿った流れを制限しながら、上流側の圧力計17aが「0.5MPa」を示す状態を開始点とし、上流側のバルブ15a及び下流側のバルブ15bを調整して、上流側の圧力計17aが「5.0MPa」を示すまで段階的に加圧していった。その加圧をしていく過程で、キャビテーションの発生の程度に応じて予め基準を定めておいたキャビテーション評点に基づいて、観察タンク16の透明窓を通してキャビテーションの発生の程度を目視で観察し、キャビテーション評点が「5」となる地点での上流側の圧力計17aが示す上流側圧力Pu及び下流側の圧力計17bが示す下流側圧力Pdを確認し、キャビテーション係数を算出した。
なお、上記キャビテーション評点は、キャビテーション未発生を「0」とし、キャビテーションが最大で発生した状態を「10」として、1刻みの11段階での評価であって、各段階での基準は、キャビテーションの発生の程度により予め定めておいたものに基づく。
また、キャビテーション係数は、下記式から算出し、その値を表1に記載した。
・キャビテーション係数=(Pd+大気圧)/(Pu-Pd)
(上記式中、Puは上流側圧力(単位:Pa)、Pdは下流側圧力(単位:Pa)である。)
上記式から算出されるキャビテーション係数が小さいほど、キャビテーションの抑制効果が高い潤滑油組成物であるといえ、キャビテーション係数の値が0.45以下である場合、キャビテーションの抑制効果に優れた潤滑油組成物と判断した。
なお、上流側圧力が0.5MPaを示す開始点において、既にキャビテーション評点が「5」以上のキャビテーションが発生している場合には、常時キャビテーションが発生しているものとし、表1では「F」と記載している。
(3) Evaluation of Cavitation Suppressing Effect FIG. 1 is a schematic diagram of a test device for evaluating the cavitation suppressing effect. The test apparatus 1 shown in FIG. 1 includes an
First, the prepared lubricating oil composition is filled in the
From the initial state, the
The above cavitation score is evaluated in 11 steps in 1 increments, with "0" for non-occurrence of cavitation and "10" for the maximum occurrence of cavitation, and the standard for each step is cavitation. Based on what is predetermined according to the degree of occurrence.
The cavitation coefficient was calculated from the following formula, and the values are shown in Table 1.
・ Cavitation coefficient = (Pd + atmospheric pressure) / (Pu-Pd)
(In the above formula, Pu is the upstream pressure (unit: Pa), and Pd is the downstream pressure (unit: Pa).)
It can be said that the smaller the cavitation coefficient calculated from the above formula is, the higher the cavitation suppressing effect is, and when the cavitation coefficient value is 0.45 or less, the lubricating oil composition is excellent in the cavitation suppressing effect. I judged it to be a thing.
If cavitation with a cavitation score of "5" or higher has already occurred at the starting point where the upstream pressure is 0.5 MPa, it is assumed that cavitation is always occurring, and "F" in Table 1. It is described as.
表1より、実施例1で調製した潤滑油組成物は、低温始動性及びせん断安定性に優れており、また、キャビテーションの抑制効果も高い結果となった。一方で、比較例1~8で調製した潤滑油組成物は、低温始動性、せん断安定性、及びキャビテーションの抑制効果のいずれかの点で劣る結果となった。 From Table 1, the lubricating oil composition prepared in Example 1 was excellent in low temperature startability and shear stability, and also had a high effect of suppressing cavitation. On the other hand, the lubricating oil compositions prepared in Comparative Examples 1 to 8 were inferior in any of the low temperature startability, shear stability, and cavitation suppressing effect.
1 試験装置
11 オイルタンク
12 ポンプ
13 ヒータ
14 流量計
15a、15b、15c バルブ
16 観察タンク
16a オリフィス
17a、17b 圧力計
18 熱電対
1
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| JPWO2015133529A1 (en) * | 2014-03-04 | 2017-04-06 | 出光興産株式会社 | Lubricating oil composition |
| JP2018104587A (en) * | 2016-12-27 | 2018-07-05 | 出光興産株式会社 | Lubricating oil composition, method for producing lubricating oil composition, and drive system device |
| JP7253528B2 (en) * | 2018-02-26 | 2023-04-06 | Eneos株式会社 | lubricating oil composition |
-
2021
- 2021-08-13 US US18/041,595 patent/US20230287293A1/en not_active Abandoned
- 2021-08-13 WO PCT/JP2021/029794 patent/WO2022039105A1/en not_active Ceased
- 2021-08-13 JP JP2022543923A patent/JPWO2022039105A1/ja active Pending
- 2021-08-13 CN CN202180037180.9A patent/CN115667472A/en active Pending
- 2021-08-13 EP EP21858252.6A patent/EP4202022A4/en not_active Withdrawn
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| See also references of EP4202022A4 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022039105A1 (en) | 2022-02-24 |
| US20230287293A1 (en) | 2023-09-14 |
| EP4202022A4 (en) | 2024-08-21 |
| EP4202022A1 (en) | 2023-06-28 |
| CN115667472A (en) | 2023-01-31 |
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