WO2023167307A1 - Lubricant composition - Google Patents

Lubricant composition Download PDF

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Publication number
WO2023167307A1
WO2023167307A1 PCT/JP2023/007952 JP2023007952W WO2023167307A1 WO 2023167307 A1 WO2023167307 A1 WO 2023167307A1 JP 2023007952 W JP2023007952 W JP 2023007952W WO 2023167307 A1 WO2023167307 A1 WO 2023167307A1
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group
ethylene
lubricating oil
oil composition
olefin copolymer
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PCT/JP2023/007952
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French (fr)
Japanese (ja)
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浩貴 金谷
昌太 阿部
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三井化学株式会社
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Publication of WO2023167307A1 publication Critical patent/WO2023167307A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene

Definitions

  • the present invention relates to a lubricating oil composition used for cooling electric motors and lubricating gears in electric vehicles.
  • Electric vehicles are a mainstream technology for such fuel saving, and electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles, for example, are expected to spread rapidly in the future.
  • An electric vehicle is characterized by being equipped with an electric motor, and is partially or wholly driven by the electric motor.
  • CVTF lubricating oil compositions.
  • These lubricating oil compositions contain a variety of additives in order to provide friction control of wet clutches and the property of suppressing wear between metals (wear resistance between metals).
  • the volume resistivity is 10. It is about ⁇ 7 ⁇ m.
  • lubricating oil compositions used in electric vehicles are required not only to have excellent wear resistance between metals, but also to maintain long-term reliability in terms of insulating properties of electric motors.
  • Patent Document 1 and Patent Document 2 propose a lubricating oil composition containing a specific phosphorus compound or a specific sulfur compound, and improve lubricating oil performance such as wear resistance and extreme pressure performance of the lubricating oil composition.
  • electrical properties such as volume resistivity are discussed.
  • In-wheel motors which drive inside the wheels of electric vehicles, are being installed as powertrains in electric vehicles and fuel cell vehicles. By embedding the motor in the wheel of the wheel, the driving force is transmitted directly to the wheel, so energy loss due to gears and drive shafts, etc., is reduced unlike conventional gasoline engine vehicles. In-wheel motors, which have low energy loss, are designed to dissipate less heat generated by the transmission and motor, so higher heat dissipation is required.
  • Patent Document 3 since the amount of lubricating oil used in in-wheel motors is smaller than that of ATF and CVTF, the viscosity tends to decrease due to severe shearing, and lubrication performance tends to be emphasized. is described.
  • Patent Document 4 the lubricating oil used in the in-wheel motor provides an in-wheel motor that can improve fuel efficiency in order to meet the needs of electric wheelchairs, etc., which want to extend the traveling distance per battery charge as much as possible.
  • housing-type systems In recent years, from the perspective of fuel efficiency in electric vehicles, so-called housing-type systems have been developed in which an electric motor and a transmission or speed reduction mechanism that transmits power from the electric motor to the drive unit are integrated in order to reduce the size and weight of the vehicle.
  • the lubricating oil As the number of vehicles using this oil is increasing, the lubricating oil is required to have a cooling function to suppress excessive heat generation of the electric motor in addition to the conventional lubricating function. Therefore, there is a demand for an improvement in the electric motor cooling performance of lubricating oil.
  • the problem to be solved by the present invention is to improve the fuel efficiency and energy saving of electric vehicles such as hybrid vehicles and electric vehicles.
  • a lubricating oil composition that has a high level of oil film retention performance at high temperatures and temperature-viscosity characteristics such as fluidity at low temperatures, and is excellent in balance, and cooling of electric motors.
  • the object is to provide a lubricating oil composition having high heat dissipation performance.
  • the present inventors have made intensive studies to develop a lubricating oil composition used for cooling an electric motor and lubricating gears in an electric vehicle having excellent performance.
  • the inventors have found that a lubricating oil composition that contains a specific ethylene- ⁇ -olefin (co)polymer and satisfies specific conditions can solve the above problems, and have completed the present invention. Specifically, the following aspects are mentioned.
  • Lubricating base oil made of (A) mineral oil having the following characteristics (A1) to (A3) and / or (B) synthetic oil having the following characteristics (B1) to (B3), (C) an ethylene- ⁇ -olefin copolymer having the characteristics of (C1) to (C5) and having a kinematic viscosity at 100°C of 4 to 10 mm 2 /s, for cooling an electric motor in an electric vehicle and A lubricating oil composition used for gear lubrication.
  • the B value represented by is 1.1 or more [2]
  • C6 Thermal diffusivity at 50° C. is 8.0 ⁇ 10 ⁇ -5 to 1.0 ⁇ 10 ⁇ -4 m ⁇ 2/s
  • C7 Volume resistivity at 50° C.
  • the content of the (C) ethylene- ⁇ -olefin copolymer when the total amount of the lubricating base oil and the (C) ethylene- ⁇ -olefin copolymer is 100% by mass is 1 to 10 mass %.
  • the lubricating oil composition of the present invention has extremely excellent temperature-viscosity characteristics as compared to conventional lubricating oils containing the same lubricating base oil, that is, high temperature-viscosity characteristics such as oil film retention at high temperatures and fluidity at low temperatures. It is a lubricating oil composition that is well-balanced, has extremely excellent shear stability, can maintain lubricating oil performance in long-term use, and has high heat dissipation performance. Suitable for cooling and gear lubrication.
  • lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention will be described in detail.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle comprises (A) a mineral oil and/or (B) a synthetic oil as a lubricating base oil, and (C ) and an ethylene- ⁇ -olefin copolymer, and is characterized by having a kinematic viscosity at 100° C. within a specific range.
  • the ethylene molar content is in the range of 30 to 70 mol%.
  • the ethylene molar content of the ethylene- ⁇ -olefin copolymer is usually 30 to 70 mol%, preferably 40 to 60 mol%, and particularly preferably. is 45 to 58 mol %. If the ethylene molar content is out of this range, crystals will form at low temperatures, the low-temperature viscosity will increase, and the fuel economy of the lubricating oil composition will deteriorate.
  • (C2) Kinematic viscosity at 100°C is 10 to 5,000 mm 2 /s
  • the kinematic viscosity at 100°C is measured by the method described in JIS K2283.
  • the ethylene- ⁇ -olefin copolymer has a kinematic viscosity at 100° C. of 10 to 5,000 mm 2 /s, preferably 20 to 4,000 mm 2 /s, more preferably 25 to 3,500 mm 2 /s. , more preferably 30 to 3,000 mm 2 /s, particularly preferably 35 to 2,500 mm 2 /s. If the kinematic viscosity at 100° C.
  • (C3) Hazen chromaticity is 30 or less This value of Hazen chromaticity is measured by the method described in JIS K0071.
  • the ethylene- ⁇ -olefin copolymer has a Hazen color of 30 or less, preferably 0-30, more preferably 0-25, still more preferably 0-20.
  • the fact that the Hazen chromaticity of the (C) ethylene- ⁇ -olefin copolymer exceeds this range means that there are too many oxygen-containing functional groups in the molecule of the (C) ethylene- ⁇ -olefin copolymer. This means that the obtained lubricating oil composition has poor heat resistance and electrical insulation.
  • the molecular weight distribution is 2.5 or less.
  • the molecular weight distribution of the ethylene- ⁇ -olefin copolymer is measured by gel permeation chromatography (GPC) according to the method described later, and is obtained by standard polystyrene conversion. It is calculated as the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained. This Mw/Mn is 2.5 or less, preferably 1.0 to 2.5, more preferably 1.0 to 2.3, still more preferably 1.0 to 2.2.
  • the molecular weight distribution exceeds this range means that it contains a large amount of low molecular weight components and high molecular weight components, and if it contains a large amount of low molecular weight components, the easily volatile components increase, and the evaporation loss increases in the lubricating oil composition. In addition, the thickening effect is lowered, and when a large amount of high molecular weight components is contained, the shear stability and heat stability of the lubricating oil composition are deteriorated.
  • the B value is 1.1 or more.
  • the B value represented by the following formula [1] of the ethylene- ⁇ -olefin copolymer is 1.1 or more, preferably 1.1 to 1. .5, more preferably 1.2 to 1.4.
  • the fact that the B value exceeds this range means that the alternating polymerization property of ethylene or ⁇ -olefin in the (C) ethylene- ⁇ -olefin copolymer is lowered, and (C) the ethylene- ⁇ -olefin copolymer
  • the coalescence crystallizes at low temperatures, deteriorating the low-temperature properties of the lubricating oil composition and significantly deteriorating fuel economy.
  • P E represents the molar fraction of the ethylene component
  • PO represents the molar fraction of the ⁇ -olefin component
  • P OE represents the molar fraction of the ethylene- ⁇ -olefin chains of all the dyad chains. rate.
  • the B value is an index indicating the randomness of the copolymerization monomer chain distribution in the copolymer
  • P E , P O and P OE in the above formula [1] are measured by 13 C-NMR spectrum, J Reports by C. Randall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], and other known documents such as "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170) can be determined based on The larger the B value, the less chain structures of ethylene and ⁇ -olefins, the more uniform the distribution of ethylene and ⁇ -olefins, and the narrower the composition distribution of the copolymer.
  • Specific measurement conditions for the B value are as described in Examples.
  • the ethylene- ⁇ -olefin copolymer preferably further has at least one characteristic of (C6) to (C8).
  • Thermal conductivity is measured at a test temperature of 50° C. in accordance with JIS R2616.
  • the specific heat is measured continuously under adiabatic conditions between 30 ° C. and 80 ° C. in an air atmosphere using a specific heat measuring device (for example, Shinku Riko SH-3000 specific heat measuring device), and the specific heat at 50 ° C. is adopted.
  • Density is measured at 50° C. in accordance with JIS K2249.
  • the thermal diffusivity at 50° C. of the ethylene- ⁇ -olefin copolymer is preferably 8.5 ⁇ 10 ⁇ -5 to 9.8 ⁇ 10 ⁇ -5m ⁇ 2/s, more preferably 8.8. ⁇ 10 ⁇ -5 to 9.6 ⁇ 10 ⁇ -5m ⁇ 2/s, more preferably 9.0 ⁇ 10 ⁇ -5 to 9.4 ⁇ 10 ⁇ -5m ⁇ 2/s.
  • the thermal diffusivity at 50° C. of (C) the ethylene- ⁇ -olefin copolymer is at least the above lower limit, the heat generation of the motor can be suppressed, and the heat resistance and electrical insulation of the lubricating oil composition are good.
  • the volume resistivity at 50°C and 250V is 1.0 x 10 ⁇ 15 to 1.0 x 10 ⁇ 17 ⁇ cm. measured at a test temperature of 50°C and 250V.
  • the volume resistivity of the ethylene- ⁇ -olefin copolymer at 50° C. and 250 V is 1.0 ⁇ 10 ⁇ 15 to 1.0 ⁇ 10 ⁇ 17 ⁇ cm, preferably 2.0 ⁇ 10 ⁇ 15 to 9.0 ⁇ 10 ⁇ 16 ⁇ cm, more preferably 3.0 ⁇ 10 ⁇ 15 to 8.0 ⁇ 10 ⁇ 16 ⁇ cm.
  • the electrical insulation of the lubricating oil composition is high, so that the safety of the electric vehicle can be maintained. can be done.
  • (C8) Relative permittivity at 50°C is 2.00 to 2.30 This value of relative permittivity at 50°C is measured at a test temperature of 50°C by the method described in JIS C2138.
  • the ethylene- ⁇ -olefin copolymer has a dielectric constant at 50°C of 2.00 to 2.30, preferably 2.00 to 2.27, and more preferably 2.00 to 2.25. is desirable.
  • the dielectric constant at 50° C. of the ethylene- ⁇ -olefin copolymer (C) is equal to or less than the above upper limit, the electrical insulation of the lubricating oil composition is high, so the safety of the electric vehicle can be maintained. .
  • the ethylene- ⁇ -olefin copolymer further preferably has at least one of the characteristics of (C9) and (C10).
  • the weight average molecular weight is 1,000 to 30,000.
  • the weight average molecular weight (Mw) of the ethylene- ⁇ -olefin copolymer is determined by gel permeation chromatography (GPC) according to the method described later. Measured and obtained by standard polystyrene conversion.
  • the weight average molecular weight (Mw) is preferably 1,200 to 25,000, more preferably 1,400 to 20,000, still more preferably 1,500 to 16,000.
  • the ethylene- ⁇ -olefin copolymer has no observed melting point in differential scanning calorimetry (DSC).
  • the melting point (Tm) is not observed means that the heat of fusion ( ⁇ H) (unit: J/g) measured by differential scanning calorimetry (DSC) is substantially not measured.
  • the fact that the heat of fusion ( ⁇ H) is not substantially measured means that no peak is observed in differential scanning calorimetry (DSC), or that the heat of fusion observed is 1 J/g or less.
  • the melting point (Tm) and heat of fusion ( ⁇ H) of the ethylene- ⁇ -olefin copolymer were measured by differential scanning calorimetry (DSC), cooled to ⁇ 100° C., and then heated at a rate of 10° C./min. It is obtained by analyzing the DSC curve with reference to JIS K7121 when the temperature is raised to 150°C. If the melting point is not observed, crystalline components do not occur at low temperatures, so an increase in low-temperature viscosity is suppressed, and the lubricating oil composition has excellent low-temperature viscosity properties.
  • DSC differential scanning calorimetry
  • (C) ⁇ -olefins used in the ethylene- ⁇ -olefin copolymer include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, C 3-20 linear or A branched ⁇ -olefin can be exemplified.
  • the ⁇ -olefin is preferably a linear or branched ⁇ -olefin having 3 to 10 carbon atoms, more preferably propylene, 1-butene, 1-hexene and 1-octene.
  • Propylene is most preferred from the standpoint of shear stability of the lubricating oil.
  • At least one other monomer selected from polar group-containing monomers, aromatic vinyl compounds, and cyclic olefins can coexist in the reaction system to proceed with polymerization.
  • Other monomers can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on a total of 100 parts by mass of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms.
  • Polar group-containing monomers include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid.
  • ⁇ , ⁇ -unsaturated carboxylic acid esters such as n-propyl, methyl methacrylate and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate; can be exemplified.
  • aromatic vinyl compounds examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, Examples include p-chlorostyrene, divinylbenzene, ⁇ -methylstyrene and allylbenzene.
  • cyclic olefins examples include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.
  • the origin of the monomer used in the ethylene- ⁇ -olefin copolymer is not particularly limited.
  • a fossil fuel-derived monomer or a biomass-derived monomer can be used. They may be used, or two or more of them may be used in combination.
  • the ethylene/ ⁇ -olefin copolymer may be composed only of a fossil fuel-derived monomer, may be composed only of a biomass-derived monomer, or may be composed of a fossil fuel-derived monomer and a biomass-derived monomer. may be used together.
  • Fossil fuels are oil, coal, natural gas, shale gas, or combinations thereof.
  • Biomass is any renewable natural raw material and its residues, such as of plant or animal origin, including fungi, yeasts, algae and bacteria.
  • the method for producing (C) the ethylene- ⁇ -olefin copolymer in the present invention is not particularly limited. and a method using a vanadium-based catalyst consisting of a compound.
  • a method for producing a copolymer with high polymerization activity metallocene compounds such as zirconocene and organic
  • a method using a catalyst system comprising an aluminum oxy compound (aluminoxane) may also be used. This method is more preferred because the chlorine content of the resulting copolymer and the 2,1-insertion of propylene can be reduced.
  • the method using a vanadium catalyst uses a greater amount of chlorine compounds in the co-catalyst, so a trace amount of chlorine may remain in the resulting ethylene- ⁇ -olefin copolymer (C). have a nature.
  • the chlorine content is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 20 ppm or less, and particularly preferably 5 ppm or less.
  • Chlorine content can be determined by various known methods. A specific measuring method in the present invention is as described in Examples.
  • the 2,1-insertion reduction of propylene makes it possible to further reduce the ethylene chains in the copolymer molecule, and the intramolecular crystallinity of ethylene can be suppressed, so the viscosity temperature characteristics of the lubricating oil composition, Low temperature viscosity characteristics can be improved.
  • an ethylene- ⁇ -olefin copolymer (C) having a good performance balance in terms of molecular weight control, molecular weight distribution, amorphousness, and B value can be obtained.
  • the (C) ethylene- ⁇ -olefin copolymer includes a bridged metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), and an organoaluminumoxy compound (b-2). ) and a compound (b-3) that forms an ion pair by reacting with the bridged metallocene compound (a) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an ⁇ -olefin having 3 to 20 carbon atoms.
  • a bridged metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), and an organoaluminumoxy compound (b-2).
  • a compound (b-3) that forms an ion pair by reacting with the bridged metallocene compound (a) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an ⁇ -ole
  • the bridged metallocene compound (a) is represented by the above formula [I]. Y, M, R 1 to R 14 , Q, n and j in formula [I] are explained below.
  • Y is a Group 14 atom, such as carbon atom, silicon atom, germanium atom and tin atom, preferably carbon atom or silicon atom, more preferably carbon atom.
  • M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.
  • R 1 to R 12 are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; , may be the same or different. Adjacent substituents of R 1 to R 12 may or may not be bonded to each other to form a ring.
  • the hydrocarbon group having 1 to 20 carbon atoms includes an alkyl group having 1 to 20 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, Examples include a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like.
  • alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group and n-hexyl.
  • the number of carbon atoms in the alkyl group is preferably 1-6.
  • saturated cyclic hydrocarbon group having 3 to 20 carbon atoms examples include a saturated cyclic hydrocarbon group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4, which are groups in which the hydrogen atoms of a cyclic saturated hydrocarbon group are replaced with hydrocarbon groups having 1 to 17 carbon atoms, such as 2-adamantyl group -cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like.
  • the cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.
  • chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). and the like, which are alkynyl groups such as ethynyl group, 1-propynyl group and 2-propynyl group (propargyl group).
  • the chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
  • cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group.
  • alkylene group having 1 to 20 carbon atoms examples include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, methylethylene group, n-propylene group and the like.
  • the alkylene group preferably has 1 to 6 carbon atoms.
  • arylene groups having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group and 4,4'-biphenylylene group.
  • the arylene group preferably has 6 to 12 carbon atoms.
  • Examples of the silicon-containing group include alkyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group, which are hydrocarbon groups having 1 to 20 carbon atoms in which the carbon atoms are replaced with silicon atoms.
  • Examples include a silyl group, an arylsilyl group such as a dimethylphenylsilyl group, a methyldiphenylsilyl group, a t-butyldiphenylsilyl group, a pentamethyldisilanyl group, and a trimethylsilylmethyl group.
  • the alkylsilyl group preferably has 1 to 10 carbon atoms
  • the arylsilyl group preferably has 6 to 18 carbon atoms.
  • examples include amino group, diethylamino group, N-morpholinyl group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group, N-morpholinyl group and nitro group.
  • the nitrogen-containing group a dimethylamino group and an N-morpholinyl group are preferred.
  • the oxygen-containing group includes a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group in which the —CH 2 — structural unit is replaced with an oxygen atom or a carbonyl group, or — Methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl, which is a group in which the CH 3 structural unit is replaced by an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n
  • halogen atoms include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.
  • halogen-containing group include a trifluoromethyl group and a tribromo group, which are groups in which hydrogen atoms are substituted by halogen atoms in the above-mentioned hydrocarbon group, silicon-containing group, nitrogen-containing group or oxygen-containing group having 1 to 20 carbon atoms. Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.
  • Q is selected in the same or different combination from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands and neutral ligands capable of coordinating with lone electron pairs.
  • the details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above.
  • a chlorine atom is preferred when Q is a halogen atom.
  • Q is a hydrocarbon group having 1 to 20 carbon atoms
  • the hydrocarbon group preferably has 1 to 7 carbon atoms.
  • anionic ligands include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.
  • Neutral ligands capable of coordinating with a lone pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like. Ether compounds and the like can be exemplified.
  • j is an integer of 1 to 4, preferably 2;
  • n is an integer of 1 to 4, preferably 1 or 2, more preferably 1.
  • R 13 and R 14 are selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; atoms or substituents, each of which may be the same or different. Also, R 13 and R 14 may be bonded to each other to form a ring, or may not be bonded to each other.
  • hydrocarbon group having 1 to 20 carbon atoms The details of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom and the halogen-containing group are as described above.
  • the aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, but is a substituent derived from an aromatic compound, namely a phenyl group, a 1-naphthyl group and a 2-naphthyl group. group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like.
  • a phenyl group or a 2-naphthyl group is preferred.
  • aromatic compounds examples include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.
  • the substituted aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but at least one hydrogen atom of the aryl group is a hydrocarbon group having 1 to 20 carbon atoms,
  • bridged metallocene compound (a) represented by formula [I] above n is preferably 1.
  • bridged metallocene compound (a-1) is represented by the following general formula [II].
  • the bridged metallocene compound (a-1) has a simpler production process and a lower production cost than the compound in which n is an integer of 2 to 4 in the above formula [I].
  • the use of 1) provides the advantage of reducing the production cost of (C) the ethylene- ⁇ -olefin copolymer.
  • bridged metallocene compound (a-2) represented by the above formula [II]
  • R 1 , R 2 , R 3 and R 4 are all preferably hydrogen.
  • Such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-2)”) is represented by the following general formula [III].
  • the bridged metallocene compound (a-2) has a lower manufacturing process than a compound in which one or more of R 1 , R 2 , R 3 and R 4 in the above formula [I] is substituted with a substituent other than a hydrogen atom. is simplified, the production cost is reduced, and the use of the crosslinked metallocene compound (a-2) further reduces the production cost of the ethylene- ⁇ -olefin copolymer (C). Further, it is generally known that the randomness of (C) an ethylene- ⁇ -olefin copolymer is reduced by carrying out high-temperature polymerization. When ethylene and one or more monomers selected from ⁇ -olefins having 3 to 20 carbon atoms are copolymerized in the presence of the It also has the advantage of being highly random.
  • either one of R 13 and R 14 is preferably an aryl group or a substituted aryl group.
  • Such a bridged metallocene compound (a-3) produces (C) an ethylene- ⁇ -olefin copolymer as compared with the case where both R 13 and R 14 are substituents other than an aryl group and a substituted aryl group.
  • one of R 13 and R 14 is more preferably an aryl group or a substituted aryl group, and the other is an alkyl group having 1 to 20 carbon atoms. It is particularly preferred that either one of R 14 is an aryl group or substituted aryl group and the other is a methyl group.
  • bridged metallocene compound (a- 4 ) the produced (C) ethylene -
  • the increase in the hydrogen partial pressure due to the introduction of hydrogen causes a decrease in the partial pressure of the olefin, which is the polymerization monomer, especially in the region where the hydrogen partial pressure is high. causes a problem of slowing down the polymerization rate. Since the polymerization reactor has a limited internal total pressure due to its design, if excessive hydrogen introduction is required especially when producing a low-molecular-weight olefin polymer, the olefin partial pressure will drop significantly. Polymerization activity may decrease.
  • the polymerization reactor is more The amount of hydrogen introduced into is reduced, the polymerization activity is improved, and the production cost of (C) the ethylene- ⁇ -olefin copolymer is reduced.
  • bridged metallocene compound (a-4) R 6 and R 11 are alkyl groups having 1 to 20 carbon atoms or An alkylene group is preferred.
  • Such a bridged metallocene compound hereinafter also referred to as “bridged metallocene compound (a-5)”) has a substituted Compared to a compound substituted with a group, the production process is simplified, the production cost is reduced, and the production cost of the (C) ethylene- ⁇ -olefin copolymer is reduced by using this crosslinked metallocene compound (a-5). has the advantage of being reduced.
  • the bridged metallocene compound (a) represented by the general formula [I], the bridged metallocene compound (a-1) represented by the general formula [II], the bridged metallocene compound represented by the general formula [III] ( In a-2) and the above bridged metallocene compounds (a-3), (a-4) and (a-5), M is more preferably a zirconium atom.
  • ⁇ 5 -tetramethyloctahydrodibenzofluorenyl which is a constituent part of the exemplified bridged metallocene compound (a), is 4,4,7,7-tetramethyl-(5a,5b,11a,12,12a- ⁇ 5 ) -1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl group
  • ⁇ 5 -octamethyloctahydrodibenzofluorenyl is 1,1,4,4, 7,7,10,10-octamethyl-(5a,5b,11a,12,12a- ⁇ 5 )-1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl each represents a group.
  • the olefin polymerization catalyst reacts with the bridged metallocene compound (a), the organometallic compound (b-1), the organoaluminum oxy compound (b-2) and the bridged metallocene compound (a) to form an ion pair. It contains at least one compound (b) selected from the group consisting of compounds (b-3).
  • organometallic compound (b-1) specifically, the following organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table are used.
  • tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum
  • Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum
  • tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum
  • triarylaluminum such as triphenylaluminum, tri(4-methylphenyl)aluminum, dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylalum
  • alkylaluminum aryloxides such as alkylaluminum aryloxides, dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and other partially hydrogenated alkylaluminums, Part
  • (b-1b) of the general formula M 2 AlR a 4 (wherein M 2 represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms); A complex alkylate of a Group 1 metal of the periodic table and aluminum represented.
  • Examples of such compounds include LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 .
  • R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; , M 3 is Mg, Zn or Cd).
  • organoaluminumoxy compound (b-2) conventionally known aluminoxanes can be used as they are. Specifically, compounds represented by the following general formula [IV] and compounds represented by the following general formula [V] can be mentioned.
  • R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.
  • methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used.
  • These aluminoxanes may be mixed with a small amount of organoaluminum compounds.
  • a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687 is also applied. be able to.
  • the "benzene-insoluble organoaluminumoxy compound” that may be used in the present invention means that the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, particularly preferably 5% or less, in terms of Al atoms. It is a compound that is 2% or less and is insoluble or sparingly soluble in benzene.
  • organoaluminumoxy compound (b-2) examples include modified methylaluminoxane represented by the following general formula [VI].
  • R is a hydrocarbon group having 1 to 10 carbon atoms, m and n each independently represent an integer of 2 or more.
  • This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum.
  • Such compounds are commonly referred to as MMAO.
  • Such MMAOs can be prepared by methods set forth in US Pat. Nos. 4,960,878 and 5,041,584.
  • Tosoh Finechem Co., Ltd. and the like also sell products prepared using trimethylaluminum and triisobutylaluminum under the names of MMAO and TMAO, in which R is an isobutyl group.
  • MMAO is an aluminoxane with improved solubility in various solvents and storage stability.
  • the compounds represented by the above formula [IV] and [V] Unlike insoluble or sparingly soluble compounds, it dissolves in aliphatic and alicyclic hydrocarbons.
  • organoaluminumoxy compound (b-2) an organoaluminumoxy compound containing boron represented by the following general formula [VII] can also be mentioned.
  • R c represents a hydrocarbon group having 1 to 10 carbon atoms.
  • R d may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • the compound (b-3) that reacts with the bridged metallocene compound (a) to form an ion pair (hereinafter sometimes abbreviated as "ionized ionic compound” or simply “ionic compound") is JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Patent Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-5321106. In addition, heteropolycompounds and isopolycompounds may also be mentioned.
  • the ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VIII].
  • R e+ includes H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like.
  • R f to R i may be the same or different, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. , preferably a substituted aryl group.
  • carbenium cations include triphenylcarbenium cations, tris(4-methylphenyl)carbenium cations, and trisubstituted carbenium cations such as tris(3,5-dimethylphenyl)carbenium cations. .
  • ammonium cation examples include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation.
  • N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, and dialkylammonium cations such as dicyclohexylammonium cations.
  • phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris(4-methylphenyl)phosphonium cations, and tris(3,5-dimethylphenyl)phosphonium cations.
  • R e+ is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.
  • compounds containing carbenium cations include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis ⁇ 3, 5-di-(trifluoromethyl)phenyl ⁇ borate, tris(4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, etc. can be exemplified.
  • compounds containing trialkyl-substituted ammonium cations include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and trimethylammonium.
  • compounds containing N,N-dialkylanilinium cations include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl ) borate, N,N-dimethylanilinium tetrakis ⁇ 3,5-di(trifluoromethyl)phenyl ⁇ borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl) Borate, N,N-diethylanilinium tetrakis ⁇ 3,5-di(trifluoromethyl)phenyl ⁇ borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N,N-2,4 , 6-pentamethylanilinium
  • di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate and the like can be exemplified as compounds containing dialkylammonium cations.
  • JP-A-2004-51676 can also be used without restriction.
  • the above ionic compound (b-3) may be used alone or in combination of two or more.
  • organometallic compound (b-1) trimethylaluminum, triethylaluminum and triisobutylaluminum, which are commercially available and readily available, are preferred. Among these, triisobutylaluminum is particularly preferable because it is easy to handle.
  • organoaluminumoxy compound (b-2) methylaluminoxane, which is a commercially available product and is readily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred.
  • MMAO which has improved solubility in various solvents and improved storage stability, is particularly preferred.
  • triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylaniline are readily available as commercial products and greatly contribute to the improvement of polymerization activity. Nium tetrakis(pentafluorophenyl)borate is preferred.
  • a combination of triisobutylaluminum and triphenylcarbenium tetrakis(pentafluorophenyl)borate, and a combination of triisobutylaluminum and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are used, since they significantly improve the polymerization activity.
  • a combination with fluorophenyl)borate is particularly preferred.
  • a carrier (c) may optionally be used as a component of the olefin polymerization catalyst.
  • the carrier (c) that may be used in the present invention is an inorganic or organic compound, and is a granular or particulate solid.
  • inorganic compounds porous oxides, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds are preferred.
  • porous oxides include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and the like, or composites or mixtures containing these, such as Using natural or synthetic zeolite, SiO2 - MgO, SiO2 - Al2O3 , SiO2 - TiO2 , SiO2 - V2O5 , SiO2 - Cr2O3 , SiO2 - TiO2 - MgO , etc. can do. Among these, those containing SiO 2 and/or Al 2 O 3 as main components are preferred. The properties of such porous oxides vary depending on the type and manufacturing method.
  • a carrier is in the range of 50-1000 m 2 /g, preferably 100-700 m 2 /g, and the pore volume is in the range of 0.3-3.0 cm 3 /g.
  • Such a carrier is used after being calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.
  • inorganic chlorides MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 and the like are used.
  • the inorganic chloride may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic chloride in a solvent such as alcohol, the inorganic chloride may be precipitated in the form of fine particles using a precipitating agent.
  • Clay is usually composed mainly of clay minerals.
  • An ion-exchangeable layered compound is a compound having a crystal structure in which planes are stacked in parallel with a weak bonding force due to ionic bonds or the like, and the ions contained therein can be exchanged.
  • Most clay minerals are ion exchange layered compounds.
  • these clays, clay minerals, and ion-exchangeable layered compounds not only naturally occurring ones but also artificially synthesized ones can be used.
  • Clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type are used as clays, clay minerals, or ion-exchangeable layered compounds.
  • Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite.
  • the ion-exchangeable layered compounds include ⁇ -Zr(HAsO 4 ) 2.H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr(KPO 4 ) 2.3H 2 O, ⁇ -Ti( HPO4 ) 2 , ⁇ -Ti( HAsO4 )2.H2O, ⁇ -Sn( HPO4 ) 2.H2O , ⁇ -Zr( HPO4 ) 2 , ⁇ - Ti ( HPO4 ) 2 and crystalline acid salts of polyvalent metals such as ⁇ -Ti(NH 4 PO 4 ) 2 ⁇ H 2 O and the like.
  • any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like.
  • Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.
  • the ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability.
  • Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars.
  • the introduction of another substance (guest compound) between the layers of a layered compound is called intercalation.
  • Guest compounds include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , metal alkoxides such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon groups), [ Al13O4 ( OH) 24 ] 7+ , [ Zr4 (OH) 14 ] 2+ , [ Fe3O ( OCOCH3 ) 6 ] + , metal hydroxide ions such as . These compounds are used singly or in combination of two or more.
  • metal alkoxides such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4 are hydrolyzed and polycondensed.
  • the resulting polymer a colloidal inorganic compound such as SiO 2 , etc., can also coexist.
  • pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.
  • clays or clay minerals preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
  • Examples of the organic compound as the carrier (c) include granular or particulate solids with a particle size in the range of 0.5 to 300 ⁇ m.
  • (co)polymers produced mainly from ⁇ -olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.
  • High-temperature polymerization is possible with a polymerization method that uses an olefin polymerization catalyst capable of producing (C) ethylene- ⁇ -olefin copolymer with high randomness. That is, by using the olefin polymerization catalyst, it is possible to suppress the decrease in the randomness of the (C) ethylene- ⁇ -olefin copolymer produced during high-temperature polymerization.
  • the viscosity of the polymerization solution containing the (C) ethylene- ⁇ -olefin copolymer produced decreases at high temperatures, so the (C) ethylene- ⁇ -olefin copolymer in the polymerization vessel is lower than during low-temperature polymerization.
  • Copolymerization of ethylene and ⁇ -olefin in the present invention can be carried out by either liquid phase polymerization method such as solution polymerization or suspension polymerization (slurry polymerization) or gas phase polymerization method.
  • Solution polymerization is particularly preferred from the viewpoint of being able to enjoy the maximum.
  • each component of the olefin polymerization catalyst is arbitrarily selected. At least two or more of each component in the catalyst may be contacted in advance.
  • the amount of the bridged metallocene compound (a) (hereinafter also referred to as “component (a)”) is generally 1 ⁇ 10 -9 to 1 ⁇ 10 -1 mol, preferably 1 ⁇ 10 -8 to 1 ⁇ 10 -1 mol, per liter of reaction volume. It is used in an amount to give 10 -2 mol.
  • the organometallic compound (b-1) (hereinafter also referred to as “component (b-1)”) has a molar ratio [( b-1)/M] is usually 0.01 to 50,000, preferably 0.05 to 10,000.
  • the organoaluminumoxy compound (b-2) (hereinafter also referred to as “component (b-2)”) is composed of the aluminum atom in component (b-2) and the transition metal atom (M) in component (a). is used in such an amount that the molar ratio [(b-2)/M] of is usually 10 to 5,000, preferably 20 to 2,000.
  • the ionic compound (b-3) (hereinafter also referred to as “component (b-3)”) has a molar ratio [( b-3)/M] is usually 1 to 10,000, preferably 1 to 5,000.
  • the polymerization temperature is usually -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, still more preferably 130°C to 200°C. In the polymerization temperature range within the above range, the higher the temperature, the lower the viscosity of the solution during polymerization, making it easier to remove the heat of polymerization.
  • the polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.
  • the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.
  • the molecular weight of the obtained copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can also be adjusted by the amount of component (b) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of copolymer produced.
  • the polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure.
  • the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. and particularly preferably hexane, heptane, octane, decane, and cyclohexane.
  • the ⁇ -olefin to be polymerized itself can also be used as a polymerization solvent.
  • Aromatic hydrocarbons such as benzene, toluene, and xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents. From the viewpoint of minimizing the impact of
  • the kinematic viscosity of olefin polymers at 100°C depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity will be high, and if the molecular weight is low, the viscosity will be low.
  • the molecular weight distribution (Mw/Mn) of the resulting polymer can be adjusted by removing low molecular weight components from the polymer obtained by a conventionally known method such as vacuum distillation.
  • the obtained polymer may be hydrogenated (hereinafter also referred to as hydrogenation) by a conventionally known method. If the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.
  • the obtained (C) ethylene- ⁇ -olefin copolymer may be used alone, or two or more of them having different molecular weights or different monomer compositions may be used in combination.
  • the ethylene- ⁇ -olefin copolymer may be graft modified with functional groups, or these may be further modified secondary.
  • the methods described in JP-A-61-126120, JP-A-2593264, etc., and secondary modification include the methods described in JP-A-2008-508402.
  • (A) Mineral oil has the following characteristics (A1) to (A3).
  • Kinematic viscosity at 100° C. is 2 to 6 mm 2 /s This value of kinematic viscosity at 100° C. is measured according to the method described in JIS K2283.
  • the kinematic viscosity at 100° C. of mineral oil is 2 to 8 mm 2 /s, preferably 2.3 to 5.5 mm 2 /s, more preferably 2.8 to 5 mm 2 /s.
  • the lubricating oil composition of the present invention is excellent in terms of the balance between volatility and temperature-viscosity characteristics.
  • Viscosity index is 105 or more This value of viscosity index is measured according to the method described in JIS K2283.
  • the mineral oil has a viscosity index of 105 or higher, preferably 110 or higher, and more preferably 115 or higher. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature-viscosity characteristics.
  • pour point is ⁇ 5° C. or less This value of pour point is measured according to the method described in ASTM D97.
  • the pour point of the mineral oil is -5°C or lower, more preferably -10°C or lower, and still more preferably -12°C or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
  • the synthetic oil has the following characteristics (B1) to (B3).
  • Kinematic viscosity at 100° C. is 1 to 9 mm 2 /s This value of kinematic viscosity at 100° C. is measured according to the method described in JIS K2283.
  • the kinematic viscosity at 100° C. of the synthetic oil is 1 to 9 mm 2 /s, preferably 1.5 to 7 mm 2 /s, more preferably 1.8 to 5 mm 2 /s.
  • the lubricating oil composition of the present invention is excellent in terms of the balance between volatility and temperature-viscosity characteristics.
  • Viscosity index is 110 or more This value of viscosity index is measured according to the method described in JIS K2283.
  • the synthetic oil has a viscosity index of 110 or higher, preferably 115 or higher, more preferably 120 or higher. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature-viscosity characteristics.
  • pour point is ⁇ 30° C. or lower This value of pour point is measured according to the method described in ASTM D97.
  • the pour point of the synthetic oil is -30°C or lower, preferably -40°C or lower, more preferably -50°C or lower, and still more preferably -60°C or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
  • the lubricating base oil used in the present invention varies in performance and quality such as viscosity characteristics, heat resistance, and oxidation stability depending on the manufacturing method and refining method, but is generally divided into mineral oil and synthetic oil.
  • API American Petroleum Institute
  • (A) Mineral oils may be any of Groups I-III in the API category and
  • Synthetic oils may be any of Groups IV and V in the API category. Details are given below.
  • the quality of the mineral oil is as described above, and the mineral oil of each quality described above can be obtained by the refining method.
  • the mineral oil specifically, the lubricating oil fraction obtained by vacuum distillation of the atmospheric residue obtained by atmospheric distillation of crude oil is subjected to solvent deasphalting, solvent extraction, hydrocracking, solvent deasphalting.
  • Lubricating base oils such as those refined by one or more treatments such as waxes, hydrorefining, or wax isomerized mineral oils can be exemplified.
  • a gas-to-liquid (GTL) base oil obtained by the Fischer-Tropsch process is also a base oil that can be suitably used as a Group III mineral oil.
  • Such GTL base oils may also be treated as Group III+ lubricant base oils, e.g. , WO00/14179, WO00/08115, WO99/41332, EP1029029, WO01/18156 and WO01/57166.
  • Poly- ⁇ -olefins belonging to Group IV are disclosed in US Pat. No. 3,382,291, US Pat. No. 3,763,244, US Pat. 780,128, US Pat. No. 4,032,591, JP-A-1-163136, US Pat. No. 4,967,032, US Pat. No. 4,926,004 It can be obtained by oligomerization with an acid catalyst such as boron trifluoride or a chromic acid catalyst. Further, a metallocene compound as described in JP-A-63-037102, JP-A-2005-200447, JP-A-2005-200448, JP-A-2009-503147, JP-A-2009-501836.
  • Poly- ⁇ -olefins are also commercially available, and those with kinematic viscosities at 100° C. of 2 mm 2 /s to 300 mm 2 /s are commercially available. Among them, it is preferable to use a poly- ⁇ -olefin of 2 to 6 mm 2 /s in that a lubricating oil composition having excellent temperature-viscosity characteristics can be obtained. Examples include the NEXBASE2000 series manufactured by NESTE, the Spectrasyn series manufactured by ExxonMobil Chemical, the Durasyn series manufactured by Ineos Oligmers, and the Synfluid series manufactured by Chevron Phillips Chemical.
  • Synthetic oils belonging to Group V include, for example, alkylbenzenes, alkylnaphthalenes, isobutene oligomers or hydrides thereof, paraffins, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, and esters.
  • alkylbenzenes and alkylnaphthalenes are usually dialkylbenzenes or dialkylnaphthalenes having an alkyl chain length of 6 to 14 carbon atoms, and such alkylbenzenes or alkylnaphthalenes are free from benzene or naphthalene and olefins. It is produced by the Delcraft alkylation reaction.
  • Alkylated olefins used in the production of alkylbenzenes or alkylnaphthalenes can be linear or branched olefins or combinations thereof. These manufacturing methods are described, for example, in US Pat. No. 3,909,432.
  • the ester is preferably a fatty acid ester from the viewpoint of compatibility with (C) the ethylene- ⁇ -olefin copolymer.
  • Fatty acid esters are not particularly limited, but include the following fatty acid esters consisting only of carbon, oxygen, and hydrogen.
  • esters include ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, tridecyl pelargonate, di-2-ethylhexyl adipate, di-2 -ethylhexyl azelate, trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane triheptanoate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, pentaerythritol tetraheptanoate, etc. .
  • the alcohol moiety constituting the ester is preferably an alcohol having a hydroxyl group of two or more functional groups, and the fatty acid moiety is a fatty acid having 8 or more carbon atoms. is preferred.
  • fatty acids with 20 or less carbon atoms which are industrially readily available, are superior in terms of production cost.
  • the fatty acid constituting the ester may be of one kind, or the effect of the present invention can be sufficiently exhibited even if a fatty acid ester produced by using a mixture of two or more kinds of acids is used.
  • fatty acid esters include trimethylolpropane lauric stearic acid mixed triesters and diisodecyl adipate, which are combined with saturated hydrocarbon components such as (C) ethylene- ⁇ -olefin copolymers.
  • saturated hydrocarbon components such as (C) ethylene- ⁇ -olefin copolymers.
  • stabilizers such as antioxidants, corrosion inhibitors, antiwear agents, friction modifiers, pour point depressants, rust inhibitors and antifoaming agents having polar groups, which will be described later.
  • the lubricating oil composition of the present invention contains 1 to 20 fatty acid esters when the total lubricating oil composition is 100% by mass when (B) synthetic oil, particularly poly- ⁇ -olefin, is used as the lubricating base oil. It is preferably included in the amount of % by mass.
  • By containing 1% by mass or more of fatty acid ester good compatibility with lubricating oil sealing materials such as resins and elastomers in electric vehicles can be obtained. Specifically, swelling of the lubricating oil sealing material can be suppressed. From the viewpoint of oxidation stability or heat resistance, the amount of ester is preferably 20% by mass or less.
  • the mineral oil itself has the effect of suppressing the swelling of the lubricating oil sealant, so the fatty acid ester is not necessarily required.
  • (B) Synthetic oil is preferable in that it is superior to (A) mineral oil in terms of heat resistance and temperature-viscosity characteristics.
  • (A) mineral oil or (B) synthetic oil may be used alone as the lubricating base oil, and (A) mineral oil and (B) synthetic oil Any mixture of two or more lubricating oils selected from may be used.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention includes (A) mineral oil and/or (B) synthetic oil and (C) ethylene- ⁇ - It contains an olefin copolymer and has the following characteristics of (D1).
  • Kinematic viscosity at 100°C is 4 to 10 mm 2 /s
  • the kinematic viscosity at 100°C (kinematic viscosity measured according to the method described in JIS K2283) is 4 to 10 mm 2 /s, preferably 4 ⁇ 7.5 mm 2 /s, more preferably 4 to 6.5 mm 2 /s, still more preferably 4.2 to 6 mm 2 /s. If the kinematic viscosity at 100° C. of the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle excessively exceeds 10 mm 2 /s, the stirring resistance of the lubricating oil to the gears, metal chains, etc. If it is excessively smaller than 4 mm 2 /s, metal contact may occur between gears or metal chains.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention preferably further has characteristics (D2) and (D3).
  • Viscosity index is 110 or more
  • This viscosity index (viscosity index measured according to the method described in JIS K2283) is preferably 110 or more, more preferably 120 or more, still more preferably 125 or more, and particularly preferably 130 or more.
  • the viscosity index is within this range, the lubricating oil composition has excellent temperature-viscosity characteristics, and it becomes possible to achieve both the energy saving property and lubricity over a wide range of temperatures.
  • the pour point is ⁇ 40° C. or less
  • the pour point of the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention (measured according to the method described in ASTM D97)
  • the pour point) is preferably ⁇ 40° C. or lower, more preferably ⁇ 45° C. or lower, and still more preferably ⁇ 50° C. or lower.
  • a low pour point indicates that the lubricating oil composition has excellent low temperature properties.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention contains 90 to 99 It is preferable to contain the (C) ethylene- ⁇ -olefin copolymer in a proportion of 10 to 1% by mass. However, the total amount of the lubricating base oil and the ethylene- ⁇ -olefin copolymer (C) is 100% by mass.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention preferably contains 92 to 99% by mass of the lubricating base oil and the (C) ethylene- ⁇ -olefin co- 8 to 1% by mass of the polymer, more preferably 95 to 99% by mass of the lubricating base oil, and 5 to 1% by mass of the (C) ethylene- ⁇ -olefin copolymer, More preferably, it contains 96 to 99% by mass of the lubricating base oil and 4 to 1% by mass of the ethylene- ⁇ -olefin copolymer (C).
  • the lubricating base oil is (A) mineral oil.
  • (A) mineral oil When the proportion of (A) mineral oil in the base oil of the lubricating oil is high, the solubility of the additives described later is excellent, and the oil is easily available and economical. More preferably 50 to 100% by mass mineral oil, and even more preferably 80 to 100% by mass mineral oil.
  • group III in the API category is preferable because it has excellent temperature-viscosity characteristics and can achieve both oil film retention at high temperatures and low torque at low temperatures.
  • 30 to 100% by mass of the lubricating base oil is (B) synthetic oil, and (B) synthetic oil is poly- ⁇ -olefin and / or ester oil aspects. It is more preferably 50 to 100% by mass of synthetic oil, and even more preferably 80 to 100% by mass of synthetic oil.
  • a high proportion of the synthetic oil (B) in the base oil of the lubricating oil is preferable because the heat resistance, temperature-viscosity characteristics, and low-temperature characteristics are excellent.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention contains extreme pressure agents, detergent-dispersants, viscosity index improvers, antioxidants, corrosion inhibitors, anti-wear agents. additives such as agents, friction modifiers, pour point depressants, rust inhibitors and defoamers.
  • additives used in the lubricating oil composition of the present invention include the following, and these can be used singly or in combination of two or more.
  • Extreme pressure agent is a general term for substances that have an effect of preventing seizure when metals are exposed to a high load, and is not particularly limited, but includes sulfides, sulfoxides, sulfones, thiophosphinates, and thiocarbonates. Sulfur-based extreme pressure agents such as sulfurized oils and fats and sulfurized olefins; etc. can be exemplified. Also, two or more of these compounds may be used in combination.
  • hydrocarbons or other organic components constituting the lubricating oil composition are carbonized by heating and shearing before the extreme pressure lubrication conditions, forming a carbide film on the metal surface.
  • the carbide coating inhibits the contact between the extreme pressure agent and the metal surface, and there is a possibility that the extreme pressure agent cannot be expected to have a sufficient effect.
  • the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention is mainly composed of saturated hydrocarbons such as copolymers. From the standpoint of dispersibility, it is preferable to add it in a state dissolved in a lubricating base oil such as a mineral oil or a synthetic hydrocarbon oil together with other additives that are used in advance.
  • a so-called additive package in which various components such as extreme pressure agent components are blended in advance and dissolved in a lubricating base oil such as mineral oil or synthetic hydrocarbon oil, is selected and added to the lubricating oil composition. A method of adding is more preferable.
  • Lubricating oils used for cooling electric motors and lubricating gears in electric vehicles contain various necessary additives for lubricating oils for automatic transmission oils and continuously variable transmission oils, and are either mineral oils or synthetic hydrocarbon oils.
  • a so-called DI package which is concentrated and dissolved in a lubricating oil such as a lubricating oil, is industrially supplied.
  • DI packages for machine oils include Lubrizol 6373 manufactured by LUBRIZOL, and these DI packages can also be applied to the lubricating oil composition of the present invention.
  • the extreme pressure agent is used in the range of 0 to 10% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • antiwear agents include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, and polytetrafluoroethylene.
  • the antiwear agent is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • Friction modifiers include amine compounds, imide compounds, and fatty acids having at least one alkyl or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl or alkenyl group having 6 to 30 carbon atoms in the molecule.
  • Examples include esters, fatty acid amides, fatty acid metal salts, and the like.
  • amine compound linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or these aliphatic Alkylene oxide adducts of group amines and the like can be exemplified.
  • imide compound include succinimide having a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms and/or modified compounds thereof with carboxylic acid, boric acid, phosphoric acid, sulfuric acid, etc. .
  • fatty acid esters include esters of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms with aliphatic monohydric alcohols or aliphatic polyhydric alcohols.
  • fatty acid amides include amides of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms and aliphatic monoamines or aliphatic polyamines.
  • fatty acid metal salts include alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms.
  • the friction modifier is used in the range of 0.01 to 5.0% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • detergent-dispersants include metal sulfonates, metal phenates, metal phosphanates, and succinimides.
  • Detergency-dispersants are used in the range of 0 to 15% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • Viscosity index improvers include ethylene- ⁇ -olefin copolymers (excluding (C) ethylene- ⁇ -olefin copolymers), olefin copolymers with a molecular weight exceeding 50,000, and methacrylate-based copolymers.
  • Known viscosity index improvers such as polymers, liquid polybutene, and poly- ⁇ -olefins having a kinematic viscosity of 15 mm 2 /s or more at 100° C. can be used in combination.
  • a viscosity index improver is used in the range of 0 to 10% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • Antioxidants include phenolic and amine compounds such as 2,6-di-t-butyl-4-methylphenol. Antioxidants are used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
  • Corrosion inhibitors include compounds such as benzotriazole, benzimidazole, and thiadiazole. Corrosion inhibitors are optionally used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition.
  • rust preventives examples include compounds such as various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, and sulfonates.
  • the antirust agent is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • antifoaming agents examples include silicone-based compounds such as dimethylsiloxane and silica gel dispersions, and alcohol-based or ester-based compounds. Antifoaming agents are used in the range of 0 to 0.2% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
  • a polymer compound containing an organic acid ester group is used, and a vinyl polymer containing an organic acid ester group is particularly preferably used.
  • Vinyl polymers containing an organic acid ester group include, for example, alkyl methacrylate (co)polymers, alkyl acrylate (co)polymers, alkyl fumarate (co)polymers, and alkyl maleate (co)polymers. Examples include polymers, alkylated naphthalenes, etc., preferably (co)polymers of alkyl acrylates, more preferably (co)polymers of alkyl acrylates ( co) polymer.
  • Such a pour point depressant has a melting point of -13°C or lower, preferably -15°C or lower, more preferably -17°C or lower.
  • the melting point of pour point depressants is measured using a differential scanning calorimeter (DSC). Specifically, about 5 mg of the sample was packed in an aluminum pan, heated to 200 ° C., held at 200 ° C. for 5 minutes, cooled to -40 ° C. at 10 ° C./min, and held at -40 ° C. for 5 minutes. After that, it is obtained from the endothermic curve when the temperature is raised at 10°C/min.
  • DSC differential scanning calorimeter
  • the pour point depressant further has a polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography in the range of 20,000 to 400,000, preferably 30,000 to 300,000, more preferably 40,000. ⁇ 200,000.
  • the pour point depressant is optionally 0 to 2% by mass, preferably 0.01 to 1% by mass, more preferably 0.02 to 0.4% by mass, based on 100% by mass of the lubricating oil composition, and further It is preferably used in the range of 0.05 to 0.35% by mass. If the amount of the pour point depressant added exceeds the above range, the shear stability of the lubricating oil composition may decrease, and lubricity may deteriorate due to the low viscosity. Moreover, the pour point depressing ability may also be impaired.
  • demulsifiers In addition to the above additives, demulsifiers, colorants, oiliness agents (oiliness improvers), etc. can be used as necessary.
  • DI packages are industrially supplied.
  • DI packages for automatic transmission oils include HITEC3419D manufactured by AFTON CHEMICAL and HITEC2426 manufactured by AFTON CHEMICAL
  • DI packages for continuously variable transmission oils include Lubrizol6373 manufactured by LUBRIZOL. but these DI packages can also be applied to the lubricating oil composition of the present invention.
  • the lubricating oil composition of the present invention can be used, for example, for cooling electric motors and lubricating gears mounted in electric vehicles such as electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles.
  • electric vehicles such as electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles.
  • the lubricating oil has extremely excellent temperature-viscosity properties, that is, oil film retention at high temperatures and low-temperature viscosity properties, and can greatly contribute to the energy saving of electric vehicles.
  • the distance between the gear and the electric motor is short, that is, it is particularly useful for an electric vehicle equipped with an in-wheel motor that requires high heat dissipation.
  • the lubricating oil composition of the present invention has extremely excellent heat dissipation performance, it has not only lubricating performance for gears and bearings of electric vehicles but also high cooling performance for electric motors.
  • the lubricating oil composition of the present invention is extremely useful for cooling electric motors and lubricating gears in electric vehicles.
  • Mw Weight average molecular weight
  • Mw/Mn molecular weight distribution
  • Molecular weight distribution was measured as follows using Tosoh Corporation HLC-8320GPC.
  • TSKgel SuperMultiporeHZ-M 4 columns
  • the column temperature was set to 40 ° C.
  • tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • the development rate was set to 0.35 ml / min
  • the sample concentration was set to The concentration was 5.5 g/L
  • the sample injection amount was 20 microliters
  • a differential refractometer was used as a detector.
  • ⁇ B value> o-Dichlorobenzene/benzene-d 6 (4/1 [vol/vol%]) was used as the measurement solvent, the measurement temperature was 120°C, the spectrum width was 250 ppm, the pulse repetition time was 5.5 seconds, and the pulse width was 4.7 ⁇ s ( 45 ° pulse) measurement conditions (100 MHz, JEOL ECX400P), or measurement temperature 120 ° C, spectrum width 250 ppm, pulse repetition time 5.5 seconds, and pulse width 5.0 ⁇ s (45 ° pulse) measurement conditions 13 C-NMR spectrum was measured at (125 MHz, Bruker Biospin AVANCE IIIcryo-500), and the B value was calculated based on the following formula [1]. Attribution of peaks was performed with reference to the above-mentioned known literature.
  • P E represents the molar fraction of the ethylene component
  • PO represents the molar fraction of the ⁇ -olefin component
  • P OE represents the molar fraction of the ethylene- ⁇ -olefin chains of all the dyad chains. rate.
  • the thermal diffusivity is expressed by the following formula by determining the thermal conductivity, specific heat, and density of the lubricating oil composition.
  • Thermal conductivity was measured at a test temperature of 50° C. in accordance with JIS R2616.
  • the specific heat was measured continuously under adiabatic conditions between 30°C and 80°C in an air atmosphere using a specific heat measuring device SH-3000 manufactured by SHINKU RIKO, and the specific heat at 50°C was adopted. Density was measured at 50° C. in accordance with JIS K2249.
  • volume resistivity was measured at a test temperature of 50° C. and 250 V according to JIS C2101.
  • ⁇ Dielectric constant> The dielectric constant was measured at a test temperature of 50°C in accordance with JIS C2138.
  • ⁇ Melting point> Using Seiko Instruments X-DSC-7000, put about 8 mg of ethylene- ⁇ -olefin copolymer in an aluminum sample pan that can be easily sealed and place it in the DSC cell. The temperature was raised to 150° C. at 10° C./min, then held at 150° C. for 5 minutes, and then lowered at 10° C./min to cool the DSC cell to ⁇ 100° C. (temperature drop process). Next, after holding at 100° C. for 5 minutes, the temperature is raised at 10° C./min. The temperature at which the enthalpy curve obtained in the heating process shows the maximum value is defined as the melting point (Tm), and the sum of the endothermic amounts accompanying melting is the melting point.
  • Tm melting point
  • Chlorine content was determined by using ICS-1600 from Thermo Fisher Scientific Co., Ltd., and ethylene- ⁇ -olefin copolymer was placed in a sample boat and burned and decomposed in an Ar/O 2 stream at a combustion furnace setting temperature of 900°C. . The generated gas at this time was absorbed into the absorbent and quantified by ion chromatography.
  • ⁇ Shear stability> The lubricating oil composition was subjected to ultrasonic irradiation for 60 minutes in accordance with JASO M347, which is an automatic transmission oil shear stability test method, and the reduction rate of kinematic viscosity at 100 ° C. due to irradiation represented by the following formula. (Viscosity reduction rate after shear test) was evaluated.
  • Ethylene- ⁇ -olefin copolymer (B) was produced according to the following polymerization examples.
  • the obtained ethylene- ⁇ -olefin copolymer (B) was hydrogenated by the following method, if necessary.
  • ⁇ Hydrogenation operation 100 mL of a hexane solution of 0.5% by mass Pd/alumina catalyst and 500 mL of a 30% by mass hexane solution of an ethylene- ⁇ -olefin copolymer were added to a 1 L stainless steel autoclave, and the autoclave was sealed and then purged with nitrogen. Ta. Then, the temperature was raised to 140° C. with stirring, and after the inside of the system was replaced with hydrogen, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.
  • the solid obtained by evaporating the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After concentrating by distilling off the solvent under reduced pressure, a small amount of hexane was added, and the mixture was allowed to stand at -20°C to precipitate a reddish orange solid. This solid was washed with a small amount of hexane and then dried under reduced pressure to obtain [methylphenylmethylene ( ⁇ 5 -cyclopentadienyl) ( ⁇ 5 -2,7-di-t-butylphenyl) as a reddish-orange solid. 1.20 g of olenyl)]zirconium dichloride are obtained.
  • Polymerization was initiated by charging a polymerization vessel with 0.00230 mmol of zirconium dichloride premixed in toluene for 15 minutes or longer. After that, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 50° C. for 15 minutes. After stopping the polymerization by adding a small amount of isobutyl alcohol into the system, unreacted monomer was purged. The resulting polymer solution was washed with 100 mL of 0.2 mol/l hydrochloric acid three times and then with 100 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight under reduced pressure at 80° C. to obtain 1.43 g of an ethylene-propylene copolymer. Furthermore, this ethylene-propylene copolymer was subjected to a hydrogenation operation to obtain a polymer 4.
  • PMA Polymethacrylate
  • PAO Evonik Poly ⁇ olefin
  • PIB Spectrasyn PAO-100 from ExxonMobil Chemical Polybutene
  • A Mineral oil; 100° C. kinematic viscosity: 3.1 mm 2 /s, viscosity index: 115, pour point: -24° C. API (American Petroleum Institute) Group II mineral oil (SK Lubricants Yubase-3)
  • Example 2 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 2 and the amount of each component added was adjusted as shown in Table 3.
  • Table 3 shows the physical properties of the lubricating oil composition.
  • Example 3 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 3 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
  • Example 4 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 4 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
  • Example 1 A lubricating oil composition was formulated in the same manner as in Example 1, except that polymer 1 was replaced with polymethacrylate (PMA), no pour point depressant was added, and the amount of each component added was adjusted as shown in Table 3. prepared. Table 3 shows the physical properties of the lubricating oil composition.
  • Example 2 A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with poly ⁇ olefin (PAO) and the amount of each component added was adjusted as shown in Table 3.
  • Table 3 shows the physical properties of the lubricating oil composition.
  • Example 3 A lubricating oil composition was formulated in the same manner as in Example 1, except that polybutene (PIB) was substituted for polymer 1 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
  • PIB polybutene
  • (A) Mineral oil is used as the lubricating base oil, and the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle contains (C) an ethylene- ⁇ -olefin copolymer. Comparing Examples 1 to 3 with Comparative Example 1 containing PMA instead of (C) ethylene- ⁇ -olefin copolymer, the lubricating oil composition of the present invention does not cause viscosity reduction even after the shear test. Therefore, the mechanism of the electric vehicle can be continuously protected for a long period of time.
  • the lubricating oil compositions of Comparative Examples 2 and 3 containing PAO or PIB instead of (C) the ethylene- ⁇ -olefin copolymer had a thermal diffusivity of less than 7.0 ⁇ 10 -2 . Therefore, sufficient motor cooling performance cannot be obtained.
  • the ethylene- ⁇ -olefin copolymer has a methylene chain as a main skeleton and has a smaller degree of freedom at the molecular ends than PAO and PIB, so heat generation due to molecular vibration is suppressed, and it was used in the lubricating oil composition. It is considered that excellent cooling or heat dissipation performance is exhibited in this case. In addition, since fluidity is poor at low temperatures, the fuel economy is remarkably inferior in low-temperature environments.

Abstract

[Problem] The present invention addresses the problem of providing a lubricant composition which has excellent shear stability and excellent temperature-viscosity characteristics in terms of fuel consumption saving and energy saving of electric vehicles, while exhibiting high heat dissipation performance. [Solution] The present invention provides a lubricant composition which has a kinematic viscosity at 100°C of 4 to 10 mm2/s and contains a lubricant base oil and an ethylene/α-olefin copolymer that has an ethylene molar content of 30% by mole to 70% by mole, a kinematic viscosity at 100°C of 10 to 5,000 mm2/s, a Hazen color number of 30 or less, a molecular weight distribution of 2.5 or less, and a B value of 1.1 or more, wherein: the lubricant base oil is composed of a mineral oil that has a kinematic viscosity at 100°C of 2 to 6 mm2/s, a viscosity index of 105 or more and a pour point of -5°C or less, and/or a synthetic oil that has a kinematic viscosity at 100°C of 1 to 9 mm2/s, a viscosity index of 110 or more and a pour point of -30°C or less. This lubricant composition is used for the purpose of cooling an electric motor and lubricating gears in an electric vehicle.

Description

潤滑油組成物lubricating oil composition
　本発明は、電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物に関するものである。 The present invention relates to a lubricating oil composition used for cooling electric motors and lubricating gears in electric vehicles.
　近年、地球環境保護の観点からＣＯ2削減が強く求められており、そのため自動車の分野においては省燃費化のための技術の開発に力が注がれている。このような省燃費化における主流の技術として電動車両があり、例えば、電気自動車、プラグインハイブリッド車、ハイブリッド車、燃料電池車が挙げられ、今後急速に普及すると予測されている。電動車両は電動モーターを備えることが特徴であり、一部または全てが電動モーターで走行する。 In recent years, there is a strong demand for CO 2 reduction from the viewpoint of protecting the global environment, and therefore, in the field of automobiles, efforts are being made to develop technologies for reducing fuel consumption. Electric vehicles are a mainstream technology for such fuel saving, and electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles, for example, are expected to spread rapidly in the future. An electric vehicle is characterized by being equipped with an electric motor, and is partially or wholly driven by the electric motor.
　変速機を有する電動車両においては、変速機と電動モーターの潤滑システムが共有化された装置用変速機が採用されることが多く、主に既存のオートマチックトランスミッションフルード（ＡＴＦ）や連続可変トランスミッションフルード（ＣＶＴＦ）が潤滑油組成物として使用されている。これらの潤滑油組成物には湿式クラッチの摩擦制御や金属同士の摩耗を抑制する特性（金属間の耐摩耗性）を付与するために多種の添加剤が配合されており、体積抵抗率は１０＾７Ωｍ程度である。また、これらの潤滑油組成物の体積抵抗率は潤滑油自体の劣化に伴って大きく低下するという問題もある。したがって、電動車両に用いる潤滑油組成物としては、金属間の耐摩耗性に優れることが要求されるだけでなく、電動モーターの絶縁性の面で長期に渡って信頼性を維持するために、電気絶縁性に優れることが要求されている。さらに、近年の省燃費性能向上ニーズ、変速機と電動モーターの潤滑システムの簡素化ニーズに起因して、潤滑油組成物には既存のＡＴＦやＣＶＴＦ以上の低粘度化が求められてきているうえ、動力伝達効率の向上や小型軽量化が求められており、変速機には、さらに高い負荷がかかるようになっている。このため絶縁性と同時に高い耐摩耗性や潤滑油組成物の剪断安定性や耐熱安定性といった耐久性能も求められるようになってきている。 In electric vehicles with transmissions, gearboxes that share a lubricating system for the transmission and the electric motor are often used. CVTF) are used as lubricating oil compositions. These lubricating oil compositions contain a variety of additives in order to provide friction control of wet clutches and the property of suppressing wear between metals (wear resistance between metals).The volume resistivity is 10. It is about ^7Ωm. In addition, there is also the problem that the volume resistivity of these lubricating oil compositions significantly decreases as the lubricating oil itself deteriorates. Therefore, lubricating oil compositions used in electric vehicles are required not only to have excellent wear resistance between metals, but also to maintain long-term reliability in terms of insulating properties of electric motors. Excellent electrical insulation is required. Furthermore, due to the recent needs for improved fuel efficiency performance and the need for simplification of lubrication systems for transmissions and electric motors, lubricating oil compositions are required to have a viscosity lower than that of existing ATFs and CVTFs. There is a demand for improved power transmission efficiency and reduction in size and weight, and a higher load is applied to the transmission. For this reason, durability performance such as high wear resistance and shear stability and heat stability of the lubricating oil composition has been required in addition to insulating properties.
　そこで、例えば特許文献１や特許文献２には特定のリン系化合物や特定の硫黄系化合物を含む潤滑油組成物が提案され、潤滑油組成物の耐摩耗性や極圧性能といった潤滑油性能に加え、体積抵抗率といった電気特性については論じられている。 Therefore, for example, Patent Document 1 and Patent Document 2 propose a lubricating oil composition containing a specific phosphorus compound or a specific sulfur compound, and improve lubricating oil performance such as wear resistance and extreme pressure performance of the lubricating oil composition. In addition, electrical properties such as volume resistivity are discussed.
　電動車両のホイールの内側で駆動するモーターとしてインホイールモーターが、電気自動車や燃料電池車などにパワートレインとして搭載されつつある。車輪のホイールにモーターを内蔵することで、駆動力がホイールへ直接伝達されることになるため、従来のガソリンエンジン自動車のようにギアや駆動軸等によるエネルギー損失が小さくなることが特徴である。エネルギー損失が小さいインホイールモーターは変速機やモーターで発生した熱を放出し難い機構のため、より高い放熱性が求められる。 In-wheel motors, which drive inside the wheels of electric vehicles, are being installed as powertrains in electric vehicles and fuel cell vehicles. By embedding the motor in the wheel of the wheel, the driving force is transmitted directly to the wheel, so energy loss due to gears and drive shafts, etc., is reduced unlike conventional gasoline engine vehicles. In-wheel motors, which have low energy loss, are designed to dissipate less heat generated by the transmission and motor, so higher heat dissipation is required.
　例えば特許文献３ではインホイールモーターに用いられる潤滑油は、ＡＴＦやＣＶＴＦに比べて少量であるため、過酷なせん断を受けることによって粘度が低下し易く、潤滑性能が特に重視される傾向であることが記載されている。特許文献４ではインホイールモーターに用いられる潤滑油はバッテリーの１充電あたりの走行距離をできるだけ延ばしたいという電動車いす等のニーズがあり、省燃費性を向上できるインホイールモーターを提供している。 For example, in Patent Document 3, since the amount of lubricating oil used in in-wheel motors is smaller than that of ATF and CVTF, the viscosity tends to decrease due to severe shearing, and lubrication performance tends to be emphasized. is described. In Patent Document 4, the lubricating oil used in the in-wheel motor provides an in-wheel motor that can improve fuel efficiency in order to meet the needs of electric wheelchairs, etc., which want to extend the traveling distance per battery charge as much as possible.
特許第５７７１５３２号公報Japanese Patent No. 5771532 特許第５７７９３７６号公報Japanese Patent No. 5779376 特開２００７－２８４５６４号公報JP 2007-284564 A 特開２０１２―２４４８１０号公報JP 2012-244810 A
　近年の電動車両では省燃費の観点から、小型、軽量化のため電動モーターと電動モーターから駆動部へ動力を伝達する変速機、または減速機構が一体となっている、いわゆる筐体型のシステムが開発され、これを採用する車輛が増加してきているため、潤滑油には従来の潤滑機能に加え電動モーターの過度な発熱を抑制する冷却機能が求められてきている。このため、潤滑油の電動モーター冷却性能の改善が求められてきている。 In recent years, from the perspective of fuel efficiency in electric vehicles, so-called housing-type systems have been developed in which an electric motor and a transmission or speed reduction mechanism that transmits power from the electric motor to the drive unit are integrated in order to reduce the size and weight of the vehicle. As the number of vehicles using this oil is increasing, the lubricating oil is required to have a cooling function to suppress excessive heat generation of the electric motor in addition to the conventional lubricating function. Therefore, there is a demand for an improvement in the electric motor cooling performance of lubricating oil.
　上記特許文献では、発熱性や放熱性抑制といった電動モーターの冷却性能については十分な議論がなされておらず、潤滑油組成物の冷却性能については未だ改良の余地がある。 The above patent documents do not sufficiently discuss the cooling performance of electric motors, such as suppressing heat generation and heat dissipation, and there is still room for improvement in the cooling performance of lubricating oil compositions.
　このような従来技術における問題点に鑑みて本発明が解決しようとする課題は、ハイブリッド自動車や電気自動車などの電気車両の省燃費化・省エネルギー化の観点から、剪断安定性が極めて優れ、かつ同一の潤滑油基油を含む従来の潤滑油に比べて、高温における油膜保持性能、および低温における流動性といった温度粘度特性が高い水準でバランスよく優れる潤滑油組成物であって、かつ電動モーターの冷却の観点から高い放熱性能を有する潤滑油組成物を提供することにある。 In view of such problems in the prior art, the problem to be solved by the present invention is to improve the fuel efficiency and energy saving of electric vehicles such as hybrid vehicles and electric vehicles. Compared to conventional lubricating oils containing lubricating oil base oils, it is a lubricating oil composition that has a high level of oil film retention performance at high temperatures and temperature-viscosity characteristics such as fluidity at low temperatures, and is excellent in balance, and cooling of electric motors. From the viewpoint of the above, the object is to provide a lubricating oil composition having high heat dissipation performance.
　本発明者らは、優れた性能を有する電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物を開発すべく鋭意検討をした結果、特定の潤滑油基油に対し、特定のエチレン－α－オレフィン（共）重合体を含有し、特定の条件を満足する潤滑油組成物が、上記課題を解決できることを見いだし、本発明を完成するに至った。具体的には、以下の態様が挙げられる。 The present inventors have made intensive studies to develop a lubricating oil composition used for cooling an electric motor and lubricating gears in an electric vehicle having excellent performance. The inventors have found that a lubricating oil composition that contains a specific ethylene-α-olefin (co)polymer and satisfies specific conditions can solve the above problems, and have completed the present invention. Specifically, the following aspects are mentioned.
　〔１〕
　以下の（Ａ１）～（Ａ３）の特徴を有する（Ａ）鉱物油、および／または以下の（Ｂ１）～（Ｂ３）の特徴を有する（Ｂ）合成油からなる潤滑油基油と、以下の（Ｃ１）～（Ｃ５）の特徴を有する（Ｃ）エチレン－α－オレフィン共重合体とを含有し、１００℃における動粘度が４～１０ｍｍ2／ｓである、電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物。
（Ａ１）１００℃における動粘度が２～６ｍｍ2／ｓであること
（Ａ２）粘度指数が１０５以上であること
（Ａ３）流動点が－５℃以下であること
（Ｂ１）１００℃における動粘度が１～９ｍｍ2／ｓであること
（Ｂ２）粘度指数が１１０以上であること
（Ｂ３）流動点が－３０℃以下であること
（Ｃ１）エチレンモル含有率が３０～７０ｍｏｌ％の範囲にあること
（Ｃ２）１００℃における動粘度が１０～５，０００ｍｍ2／ｓであること
（Ｃ３）ハーゼン色度が３０以下であること
（Ｃ４）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、ポリスチレン換算により得られた分子量において、分子量分布（Ｍｗ／Ｍｎ）が２．５以下であること
（Ｃ５）下記式［１］ [1]
Lubricating base oil made of (A) mineral oil having the following characteristics (A1) to (A3) and / or (B) synthetic oil having the following characteristics (B1) to (B3), (C) an ethylene-α-olefin copolymer having the characteristics of (C1) to (C5) and having a kinematic viscosity at 100°C of 4 to 10 mm 2 /s, for cooling an electric motor in an electric vehicle and A lubricating oil composition used for gear lubrication.
(A1) Kinematic viscosity at 100°C is 2 to 6 mm 2 /s (A2) Viscosity index is 105 or more (A3) Pour point is -5°C or less (B1) Kinematic viscosity at 100°C ( B2 ) Viscosity index is 110 or more (B3) Pour point is -30°C or less (C1) Ethylene molar content is in the range of 30 to 70 mol% (C2) Kinematic viscosity at 100° C. of 10 to 5,000 mm 2 /s (C3) Hazen chromaticity of 30 or less (C4) Measured by gel permeation chromatography (GPC) and converted to polystyrene In the obtained molecular weight, the molecular weight distribution (Mw / Mn) is 2.5 or less (C5) the following formula [1]
Figure JPOXMLDOC01-appb-M000002
 （式中、ＰEはエチレン成分の含有モル分率を示し、ＰOはα－オレフィン成分の含有モル分率を示し、ＰOEは全ｄｙａｄ連鎖のエチレン－α－オレフィン連鎖のモル分率を示す。）
で表されるＢ値が、１．１以上であること
　〔２〕
　前記（Ｃ）エチレン－α－オレフィン共重合体が以下の（Ｃ６）～（Ｃ８）のいずれか１つ以上の特徴を有する上記〔１〕に記載の潤滑油組成物。
（Ｃ６）５０℃における熱拡散率が８．０×１０＾－５～１．０×１０＾－４ｍ＾２／ｓであること
（Ｃ７）５０℃、２５０Ｖにおける体積抵抗率が１．０×１０＾１５～１．０×１０＾１７Ω・ｃｍであること
（Ｃ８）５０℃における比誘電率が２．００～２．３０であること
　〔３〕
　前記（Ｃ）エチレン－α－オレフィン共重合体のエチレンモル含有率が４０～６０ｍｏｌ％の範囲にある上記〔１〕または〔２〕に記載の潤滑油組成物。
Figure JPOXMLDOC01-appb-M000002
 (In the formula, P E indicates the molar fraction of the ethylene component, PO indicates the molar fraction of the α-olefin component, and P OE indicates the molar fraction of the ethylene-α-olefin chain of all the dyad chains. show.)
The B value represented by is 1.1 or more [2]
The lubricating oil composition according to [1] above, wherein (C) the ethylene-α-olefin copolymer has one or more of the following characteristics of (C6) to (C8).
(C6) Thermal diffusivity at 50° C. is 8.0×10^-5 to 1.0×10^-4 m^2/s (C7) Volume resistivity at 50° C. and 250 V is 1.0× 10̂15 to 1.0×10̂17Ω·cm (C8) Relative permittivity at 50°C is 2.00 to 2.30 [3]
The lubricating oil composition according to [1] or [2] above, wherein the ethylene molar content of the ethylene-α-olefin copolymer (C) is in the range of 40 to 60 mol %.
　〔４〕
　前記（Ｃ）エチレン－α－オレフィン共重合体の１００℃における動粘度が２０～２，５００ｍｍ2／ｓである上記〔１〕～〔３〕のいずれかに記載の潤滑油組成物。 [4]
The lubricating oil composition according to any one of [1] to [3] above, wherein the (C) ethylene-α-olefin copolymer has a kinematic viscosity at 100° C. of 20 to 2,500 mm 2 /s.
　〔５〕
　前記（Ｃ）エチレン－α－オレフィン共重合体のα－オレフィンがプロピレンである上記〔１〕～〔４〕のいずれかに記載の潤滑油組成物。 [5]
The lubricating oil composition according to any one of [1] to [4] above, wherein the α-olefin of the ethylene-α-olefin copolymer (C) is propylene.
　〔６〕
　前記潤滑油基油と前記（Ｃ）エチレン－α－オレフィン共重合体との合計量を１００質量％とした場合の前記（Ｃ）エチレン－α－オレフィン共重合体の含有量が１～１０質量％である上記〔１〕～〔５〕のいずれかに記載の潤滑油組成物。 [6]
The content of the (C) ethylene-α-olefin copolymer when the total amount of the lubricating base oil and the (C) ethylene-α-olefin copolymer is 100% by mass is 1 to 10 mass %. The lubricating oil composition according to any one of [1] to [5] above.
　〔７〕
　前記電動車両が電気自動車、プラグインハイブリッド車、ハイブリッド車、燃料電池車である上記〔１〕～〔６〕のいずれかに記載の潤滑油組成物。 [7]
The lubricating oil composition according to any one of [1] to [6] above, wherein the electric vehicle is an electric vehicle, a plug-in hybrid vehicle, a hybrid vehicle, or a fuel cell vehicle.
　〔７ａ〕
　前記電動車両がハイブリッド車または電気自動車である上記〔７〕に記載の潤滑油組成物。 [7a]
The lubricating oil composition according to [7] above, wherein the electric vehicle is a hybrid vehicle or an electric vehicle.
　〔８〕
　前記電動車両に装備された電気モーターがインホイールモーターである上記〔１〕～〔６〕のいずれかに記載の潤滑油組成物。 [8]
The lubricating oil composition according to any one of [1] to [6] above, wherein the electric motor installed in the electric vehicle is an in-wheel motor.
　〔９〕
　前記電動車両が電動車いす、電動カートである上記〔１〕～〔６〕のいずれかに記載の潤滑油組成物。 [9]
The lubricating oil composition according to any one of [1] to [6] above, wherein the electric vehicle is an electric wheelchair or an electric cart.
　〔１０〕
　前記電動車両が電動スケートボード、電動ローラースケートである上記〔１〕～〔６〕のいずれかに記載の潤滑油組成物。 [10]
The lubricating oil composition according to any one of [1] to [6] above, wherein the electric vehicle is an electric skateboard or an electric roller skate.
　本発明の潤滑油組成物は、同一の潤滑油基油を含む従来の潤滑油に比べて温度粘度特性が極めて優れ、すなわち高温での油膜保持性および低温における流動性といった温度粘度特性が高い水準でバランスよく優れ、かつ剪断安定性が極めて優れ、長期間の使用において潤滑油性能を維持可能な潤滑油組成物であり、加えて高い放熱性能を有しているため、電動車両における電動モーターの冷却および歯車の潤滑に好適に適用できる。 The lubricating oil composition of the present invention has extremely excellent temperature-viscosity characteristics as compared to conventional lubricating oils containing the same lubricating base oil, that is, high temperature-viscosity characteristics such as oil film retention at high temperatures and fluidity at low temperatures. It is a lubricating oil composition that is well-balanced, has extremely excellent shear stability, can maintain lubricating oil performance in long-term use, and has high heat dissipation performance. Suitable for cooling and gear lubrication.
　以下、本発明に係る電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物（以下、単に「潤滑油組成物」ともいう。）について詳細に説明する。 Hereinafter, the lubricating oil composition (hereinafter also simply referred to as "lubricating oil composition") used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention will be described in detail.
　［電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物］
　本発明に係る電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は、（Ａ）鉱物油、および／または（Ｂ）合成油からなる潤滑油基油と、（Ｃ）エチレン－α－オレフィン共重合体とを含有し、１００℃における動粘度が特定の範囲にあることを特徴としている。 [Lubricating Oil Composition Used for Cooling Electric Motors and Lubricating Gears in Electric Vehicles]
The lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention comprises (A) a mineral oil and/or (B) a synthetic oil as a lubricating base oil, and (C ) and an ethylene-α-olefin copolymer, and is characterized by having a kinematic viscosity at 100° C. within a specific range.
　＜（Ｃ）エチレン－α－オレフィン共重合体＞
　　（Ｃ）エチレン－α－オレフィン共重合体は以下（Ｃ１）～（Ｃ５）の特徴を有する。 <(C) Ethylene-α-olefin copolymer>
(C) The ethylene-α-olefin copolymer has the following characteristics (C1) to (C5).
　（Ｃ１）エチレンモル含有率が３０～７０ｍｏｌ％の範囲にあること
　（Ｃ）エチレン－α－オレフィン共重合体のエチレンモル含有率は、通常３０～７０モル％、好ましくは４０～６０モル％、特に好ましくは４５～５８モル％である。エチレンモル含有率がこの範囲を外れると、低温で結晶が生じ、低温粘度が上昇し、潤滑油組成物の省燃費性が悪化する。 (C1) The ethylene molar content is in the range of 30 to 70 mol%. (C) The ethylene molar content of the ethylene-α-olefin copolymer is usually 30 to 70 mol%, preferably 40 to 60 mol%, and particularly preferably. is 45 to 58 mol %. If the ethylene molar content is out of this range, crystals will form at low temperatures, the low-temperature viscosity will increase, and the fuel economy of the lubricating oil composition will deteriorate.
　（Ｃ）エチレン－α－オレフィン共重合体のエチレンモル含有率は、「高分子分析ハンドブック」（朝倉書店　発行　Ｐ１６３～１７０）に記載の方法に従って13Ｃ－ＮＭＲで測定される。また、この方法により求められた試料を既知試料として、フーリエ変換赤外分光（ＦＴ－ＩＲ）を用いて測定することも可能である。 (C) The ethylene molar content of the ethylene-α-olefin copolymer is measured by 13 C-NMR according to the method described in "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170). It is also possible to measure the sample obtained by this method as a known sample using Fourier transform infrared spectroscopy (FT-IR).
　（Ｃ２）１００℃における動粘度が１０～５，０００ｍｍ2／ｓであること
　この１００℃における動粘度の値はＪＩＳ Ｋ２２８３に記載の方法により測定した場合のものである。（Ｃ）エチレン－α－オレフィン共重合体の１００℃における動粘度は、１０～５，０００ｍｍ2／ｓ、好ましくは２０～４，０００ｍｍ2／ｓ、より好ましくは２５～３，５００ｍｍ2／ｓ、さらに好ましくは３０～３，０００ｍｍ2／ｓ、特に好ましくは３５～２，５００ｍｍ2／ｓである。（Ｃ）エチレン－α－オレフィン共重合体の１００℃における動粘度が上記範囲を上回ると、潤滑油組成物の剪断安定性が低下し、省燃費性が悪化する。上記範囲を下回ると、低温流動性が悪化し、低温環境下での始動時に著しく燃費が悪化する。 (C2) Kinematic viscosity at 100°C is 10 to 5,000 mm 2 /s The kinematic viscosity at 100°C is measured by the method described in JIS K2283. (C) The ethylene-α-olefin copolymer has a kinematic viscosity at 100° C. of 10 to 5,000 mm 2 /s, preferably 20 to 4,000 mm 2 /s, more preferably 25 to 3,500 mm 2 /s. , more preferably 30 to 3,000 mm 2 /s, particularly preferably 35 to 2,500 mm 2 /s. If the kinematic viscosity at 100° C. of the (C) ethylene-α-olefin copolymer exceeds the above range, the shear stability of the lubricating oil composition will deteriorate, resulting in poor fuel economy. Below the above range, the low-temperature fluidity deteriorates, and the fuel consumption significantly deteriorates at the time of start-up in a low-temperature environment.
　（Ｃ３）ハーゼン色度が３０以下であること
　このハーゼン色度の値はＪＩＳ Ｋ００７１に記載の方法により測定した場合のものである。（Ｃ）エチレン－α－オレフィン共重合体のハーゼン色度は、３０以下、好ましくは０～３０、より好ましくは０～２５、さらに好ましくは０～２０である。（Ｃ）エチレン－α－オレフィン共重合体のハーゼン色度がこの範囲を超えるということは、（Ｃ）エチレン－α－オレフィン共重合体の分子中に酸素含有官能基が過多に存在することを意味し、得られる潤滑油組成物の耐熱性、電気絶縁性が悪化する。 (C3) Hazen chromaticity is 30 or less This value of Hazen chromaticity is measured by the method described in JIS K0071. (C) The ethylene-α-olefin copolymer has a Hazen color of 30 or less, preferably 0-30, more preferably 0-25, still more preferably 0-20. The fact that the Hazen chromaticity of the (C) ethylene-α-olefin copolymer exceeds this range means that there are too many oxygen-containing functional groups in the molecule of the (C) ethylene-α-olefin copolymer. This means that the obtained lubricating oil composition has poor heat resistance and electrical insulation.
　（Ｃ４）分子量分布が２．５以下であること
　（Ｃ）エチレン－α－オレフィン共重合体の分子量分布は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって後述する方法に従い測定し、標準ポリスチレン換算により得られた重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）として算出される。このＭｗ／Ｍｎは２．５以下、好ましくは１．０～２．５、より好ましくは１．０～２．３、さらに好ましくは１．０～２．２である。分子量分布がこの範囲を超えるということは、低分子量成分や高分子量成分を多く含むということであり、低分子量成分を多く含む場合は易揮発成分が増加し、潤滑油組成物において蒸発減量が増大し、かつ増粘効果が低下し、高分子量成分を多く含む場合は潤滑油組成物の剪断安定性・耐熱安定性の悪化が生じる。 (C4) The molecular weight distribution is 2.5 or less. (C) The molecular weight distribution of the ethylene-α-olefin copolymer is measured by gel permeation chromatography (GPC) according to the method described later, and is obtained by standard polystyrene conversion. It is calculated as the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained. This Mw/Mn is 2.5 or less, preferably 1.0 to 2.5, more preferably 1.0 to 2.3, still more preferably 1.0 to 2.2. The fact that the molecular weight distribution exceeds this range means that it contains a large amount of low molecular weight components and high molecular weight components, and if it contains a large amount of low molecular weight components, the easily volatile components increase, and the evaporation loss increases in the lubricating oil composition. In addition, the thickening effect is lowered, and when a large amount of high molecular weight components is contained, the shear stability and heat stability of the lubricating oil composition are deteriorated.
　（Ｃ５）Ｂ値が１．１以上であること
　（Ｃ）エチレン－α－オレフィン共重合体の下記式［１］で表されるＢ値は、１．１以上、好ましくは１．１～１．５、より好ましくは１．２～１．４である。Ｂ値がこの範囲を超えるということは、（Ｃ）エチレン－α－オレフィン共重合体のエチレン、若しくはα－オレフィンの交互重合性が低下することを表し、（Ｃ）エチレン－α－オレフィン共重合体が低温下で結晶化し、潤滑油組成物の低温特性が悪化し、著しく省燃費性が悪化する。 (C5) The B value is 1.1 or more. (C) The B value represented by the following formula [1] of the ethylene-α-olefin copolymer is 1.1 or more, preferably 1.1 to 1. .5, more preferably 1.2 to 1.4. The fact that the B value exceeds this range means that the alternating polymerization property of ethylene or α-olefin in the (C) ethylene-α-olefin copolymer is lowered, and (C) the ethylene-α-olefin copolymer The coalescence crystallizes at low temperatures, deteriorating the low-temperature properties of the lubricating oil composition and significantly deteriorating fuel economy.
Figure JPOXMLDOC01-appb-M000003
 　式［１］中、ＰEはエチレン成分の含有モル分率を示し、ＰOはα－オレフィン成分の含有モル分率を示し、ＰOEは全ｄｙａｄ連鎖のエチレン－α－オレフィン連鎖のモル分率を示す。
Figure JPOXMLDOC01-appb-M000003
 In formula [1], P E represents the molar fraction of the ethylene component, PO represents the molar fraction of the α-olefin component, and P OE represents the molar fraction of the ethylene-α-olefin chains of all the dyad chains. rate.
　Ｂ値は、共重合体中における共重合モノマー連鎖分布のランダム性を示す指標であり、上記式［１］中のＰE、ＰOおよびＰOEは、13Ｃ－ＮＭＲスペクトルを測定し、Ｊ. Ｃ. Ｒａｎｄａｌｌ ［Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ， １５， ３５３ （１９８２）］、Ｊ.Ｒａｙ ［Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ， １０， ７７３ （１９７７）］らの報告、「高分子分析ハンドブック」（朝倉書店　発行　Ｐ１６３～１７０）等の公知文献に基づいて求めることができる。上記Ｂ値が大きいほど、エチレンおよびα－オレフィンの連鎖構造が少なく、エチレンおよびα－オレフィンの分布が一様であり、組成分布の狭い共重合体であることを示している。その結果、Ｂ値が大きいほど（Ｃ）エチレン－α－オレフィン共重合体の流動点が低くなり、潤滑油組成物が良好な低温粘度特性を示す。Ｂ値の具体的な測定条件は実施例に記載した通りである。 The B value is an index indicating the randomness of the copolymerization monomer chain distribution in the copolymer, and P E , P O and P OE in the above formula [1] are measured by 13 C-NMR spectrum, J Reports by C. Randall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)], and other known documents such as "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170) can be determined based on The larger the B value, the less chain structures of ethylene and α-olefins, the more uniform the distribution of ethylene and α-olefins, and the narrower the composition distribution of the copolymer. As a result, the larger the B value, the lower the pour point of the ethylene-α-olefin copolymer (C), and the lubricating oil composition exhibits good low-temperature viscosity characteristics. Specific measurement conditions for the B value are as described in Examples.
　（Ｃ）エチレン－α－オレフィン共重合体はさらに（Ｃ６）～（Ｃ８）の少なくとも１つの特徴を有することが好ましい。 (C) The ethylene-α-olefin copolymer preferably further has at least one characteristic of (C6) to (C8).
　（Ｃ６）５０℃における熱拡散率が８．０×１０＾－５～１．０×１０＾－４ｍ＾２／ｓであること
　この５０℃における熱拡散率の値は熱伝導率、比熱、密度をそれぞれ求めることで以下の式で表される。 (C6) The thermal diffusivity at 50°C is 8.0 x 10^-5 to 1.0 x 10^-4 m^2/s. It is represented by the following formula by obtaining the respective densities.
Figure JPOXMLDOC01-appb-M000004
 　熱伝導率は、ＪＩＳ　Ｒ２６１６に準拠し試験温度５０℃において測定する。比熱は、比熱測定装置（例えば、真空理工製比熱測定装置ＳＨ－３０００型）を用い、空気雰囲気下において３０℃から８０℃の間において断熱条件において連続で測定し、５０℃における比熱を採用する。密度は、ＪＩＳ　Ｋ２２４９に準拠し５０℃において測定する。
Figure JPOXMLDOC01-appb-M000004
 Thermal conductivity is measured at a test temperature of 50° C. in accordance with JIS R2616. The specific heat is measured continuously under adiabatic conditions between 30 ° C. and 80 ° C. in an air atmosphere using a specific heat measuring device (for example, Shinku Riko SH-3000 specific heat measuring device), and the specific heat at 50 ° C. is adopted. . Density is measured at 50° C. in accordance with JIS K2249.
　（Ｃ）エチレン－α－オレフィン共重合体の５０℃における熱拡散率は、好ましくは８．５×１０＾－５～９．８×１０＾－５ｍ＾２／ｓ、より好ましくは８．８×１０＾－５～９．６×１０＾－５ｍ＾２／ｓ、さらに好ましくは９．０×１０＾－５～９．４×１０＾－５ｍ＾２／ｓであることが望ましい。（Ｃ）エチレン－α－オレフィン共重合体の５０℃における熱拡散率が上記下限値以上であると、モーターの発熱を抑えられ、潤滑油組成物の耐熱性および電気絶縁性が良好である。 (C) The thermal diffusivity at 50° C. of the ethylene-α-olefin copolymer is preferably 8.5×10̂-5 to 9.8×10̂-5m̂2/s, more preferably 8.8. ×10^-5 to 9.6×10^-5m^2/s, more preferably 9.0×10^-5 to 9.4×10^-5m^2/s. When the thermal diffusivity at 50° C. of (C) the ethylene-α-olefin copolymer is at least the above lower limit, the heat generation of the motor can be suppressed, and the heat resistance and electrical insulation of the lubricating oil composition are good.
　（Ｃ７）５０℃、２５０Ｖにおける体積抵抗率が１．０×１０＾１５～１．０×１０＾１７Ω・ｃｍであること
　この５０℃、２５０Ｖにおける体積抵抗率の値はＪＩＳ　Ｃ２１０１に記載の方法により試験温度５０℃、２５０Ｖにおいて測定した場合のものである。（Ｃ）エチレン－α－オレフィン共重合体の５０℃、２５０Ｖにおける体積抵抗率は、１．０×１０＾１５～１．０×１０＾１７Ω・ｃｍ、好ましくは２．０×１０＾１５～９．０×１０＾１６Ω・ｃｍ、より好ましくは３．０×１０＾１５～８．０×１０＾１６Ω・ｃｍであることが望ましい。（Ｃ）エチレン－α－オレフィン共重合体の５０℃、２５０Ｖにおける体積抵抗率が上記下限値以上であると、潤滑油組成物の電気絶縁性が高いため、電動車両の安全性を維持することができる。 (C7) The volume resistivity at 50°C and 250V is 1.0 x 10^15 to 1.0 x 10^17 Ω cm. measured at a test temperature of 50°C and 250V. (C) The volume resistivity of the ethylene-α-olefin copolymer at 50° C. and 250 V is 1.0×10̂15 to 1.0×10̂17 Ω·cm, preferably 2.0×10̂15 to 9.0×10̂16 Ω·cm, more preferably 3.0×10̂15 to 8.0×10̂16 Ω·cm. (C) When the volume resistivity of the ethylene-α-olefin copolymer at 50° C. and 250 V is equal to or higher than the above lower limits, the electrical insulation of the lubricating oil composition is high, so that the safety of the electric vehicle can be maintained. can be done.
　（Ｃ８）５０℃における比誘電率が２．００～２．３０であること
　この５０℃における比誘電率の値はＪＩＳ　Ｃ２１３８に記載の方法により試験温度５０℃において測定した場合のものである。（Ｃ）エチレン－α－オレフィン共重合体の５０℃における比誘電率は、２．００～２．３０、好ましくは２．００～２．２７、より好ましくは２．００～２．２５であることが望ましい。（Ｃ）エチレン－α－オレフィン共重合体の５０℃における比誘電率が上記上限値以下であると、潤滑油組成物の電気絶縁性が高いため、電動車両の安全性を維持することができる。 (C8) Relative permittivity at 50°C is 2.00 to 2.30 This value of relative permittivity at 50°C is measured at a test temperature of 50°C by the method described in JIS C2138. (C) The ethylene-α-olefin copolymer has a dielectric constant at 50°C of 2.00 to 2.30, preferably 2.00 to 2.27, and more preferably 2.00 to 2.25. is desirable. When the dielectric constant at 50° C. of the ethylene-α-olefin copolymer (C) is equal to or less than the above upper limit, the electrical insulation of the lubricating oil composition is high, so the safety of the electric vehicle can be maintained. .
　（Ｃ）エチレン－α－オレフィン共重合体はさらに（Ｃ９）、（Ｃ１０）の少なくとも１つの特徴を有することよりが好ましい。 (C) The ethylene-α-olefin copolymer further preferably has at least one of the characteristics of (C9) and (C10).
　（Ｃ９）重量平均分子量が１，０００～３０，０００であること
　（Ｃ）エチレン－α－オレフィン共重合体の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって後述する方法に従い測定し、標準ポリスチレン換算により得られる。この重量平均分子量（Ｍｗ）は好ましくは１，２００～２５，０００であり、より好ましくは１，４００～２０，０００であり、さらに好ましくは１，５００～１６，０００である。（Ｃ）エチレン－α－オレフィン共重合体の重量平均分子量（Ｍｗ）が１，０００以上であると、易揮発成分が少ないため、潤滑油組成物において蒸発減量が少なく、かつ増粘効果、温度粘度特性が優れ、３０，０００以下であると、潤滑油組成物は、流動点が低く、剪断安定性、耐熱性に優れる。 (C9) The weight average molecular weight is 1,000 to 30,000. (C) The weight average molecular weight (Mw) of the ethylene-α-olefin copolymer is determined by gel permeation chromatography (GPC) according to the method described later. Measured and obtained by standard polystyrene conversion. The weight average molecular weight (Mw) is preferably 1,200 to 25,000, more preferably 1,400 to 20,000, still more preferably 1,500 to 16,000. (C) When the weight average molecular weight (Mw) of the ethylene-α-olefin copolymer is 1,000 or more, since there are few easily volatile components, the evaporation loss in the lubricating oil composition is small, and the thickening effect, temperature When the viscosity is 30,000 or less, the lubricating oil composition has a low pour point and excellent shear stability and heat resistance.
　（Ｃ１０）融点が観測されないこと
　（Ｃ）エチレン－α－オレフィン共重合体には示差走査熱量測定（ＤＳＣ）において融点が観測されないことが好ましい。ここで、融点（Ｔｍ）が観測されないとは、示差走査熱量測定（ＤＳＣ）で測定される融解熱量（ΔＨ）（単位：Ｊ／ｇ）が実質的に計測されないことをいう。融解熱量（ΔＨ）が実質的に計測されないとは、示差走査熱量測定（ＤＳＣ）おいてピークが観測されないか、あるいは観測された融解熱量が１Ｊ／ｇ以下であることである。（Ｃ）エチレン－α－オレフィン共重合体の融点（Ｔｍ）および融解熱量（ΔＨ）は、示差走査熱量測定（ＤＳＣ）を行い、－１００℃まで冷却してから昇温速度１０℃／分で１５０℃まで昇温したときにＤＳＣ曲線をＪＩＳ　Ｋ７１２１を参考に解析し求められる。融点が観測されないと低温で結晶成分が生じないため低温粘度の上昇が抑制され、潤滑油組成物は低温粘度特性に優れる。 (C10) No melting point observed (C) It is preferable that the ethylene-α-olefin copolymer has no observed melting point in differential scanning calorimetry (DSC). Here, the melting point (Tm) is not observed means that the heat of fusion (ΔH) (unit: J/g) measured by differential scanning calorimetry (DSC) is substantially not measured. The fact that the heat of fusion (ΔH) is not substantially measured means that no peak is observed in differential scanning calorimetry (DSC), or that the heat of fusion observed is 1 J/g or less. (C) The melting point (Tm) and heat of fusion (ΔH) of the ethylene-α-olefin copolymer were measured by differential scanning calorimetry (DSC), cooled to −100° C., and then heated at a rate of 10° C./min. It is obtained by analyzing the DSC curve with reference to JIS K7121 when the temperature is raised to 150°C. If the melting point is not observed, crystalline components do not occur at low temperatures, so an increase in low-temperature viscosity is suppressed, and the lubricating oil composition has excellent low-temperature viscosity properties.
　（Ｃ）エチレン－α－オレフィン共重合体に用いられるα－オレフィンとしては、プロピレン、１－ブテン、１－ペンテン、３－メチル－１－ブテン、１－ヘキセン、４－メチル－１－ペンテン、３－メチル－１－ペンテン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン、１－エイコセン、ビニルシクロヘキサンなどの炭素数３～２０の直鎖状または分岐状のα－オレフィンを例示することができる。α－オレフィンとしては、炭素数３～１０の直鎖状または分岐状のα－オレフィンが好ましく、プロピレン、１－ブテン、１－ヘキセンおよび１－オクテンがより好ましく、得られる共重合体を用いた潤滑油の剪断安定性の点からプロピレンが最も好ましい。これらのα－オレフィンは１種単独で、または２種以上組み合わせて用いることができる。 (C) α-olefins used in the ethylene-α-olefin copolymer include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, C 3-20 linear or A branched α-olefin can be exemplified. The α-olefin is preferably a linear or branched α-olefin having 3 to 10 carbon atoms, more preferably propylene, 1-butene, 1-hexene and 1-octene. Propylene is most preferred from the standpoint of shear stability of the lubricating oil. These α-olefins can be used singly or in combination of two or more.
　また、極性基含有モノマー、芳香族ビニル化合物、および環状オレフィンから選択される少なくとも１種の他のモノマーを反応系に共存させて重合を進めることもできる。エチレンおよび炭素数が３～２０のα－オレフィンとの合計１００質量部に対して、他のモノマーは、例えば２０質量部以下、好ましくは１０質量部以下の量で用いることができる。 Also, at least one other monomer selected from polar group-containing monomers, aromatic vinyl compounds, and cyclic olefins can coexist in the reaction system to proceed with polymerization. Other monomers can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on a total of 100 parts by mass of ethylene and an α-olefin having 3 to 20 carbon atoms.
　極性基含有モノマーとしては、アクリル酸、メタクリル酸、フマル酸、無水マレイン酸などのα，β－不飽和カルボン酸類、およびこれらのナトリウム塩等の金属塩類、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、メタクリル酸メチル、メタクリル酸エチルなどのα，β－不飽和カルボン酸エステル類、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類、アクリル酸グリシジル、メタクリル酸グリシジルなどの不飽和グリシジル類などを例示することができる。 Polar group-containing monomers include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic anhydride, metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid. α,β-unsaturated carboxylic acid esters such as n-propyl, methyl methacrylate and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate; can be exemplified.
　芳香族ビニル化合物としては、スチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ｏ，ｐ－ジメチルスチレン、メトキシスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルベンジルアセテート、ヒドロキシスチレン、ｐ－クロロスチレン、ジビニルベンゼン、α－メチルスチレン、アリルベンゼンなどを例示することができる。 Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, Examples include p-chlorostyrene, divinylbenzene, α-methylstyrene and allylbenzene.
　環状オレフィンとしては、シクロペンテン、シクロヘプテン、ノルボルネン、５－メチル－２－ノルボルネン、テトラシクロドデセンなどの炭素数３～３０、好ましくは３～２０の環状オレフィン類を例示することができる。 Examples of cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, and tetracyclododecene.
　（Ｃ）エチレン－α－オレフィン共重合体に用いられるモノマーの由来に特に制限はないが、例えば、化石燃料由来のモノマーもしくはバイオマス由来のモノマーを用いることができ、これらのモノマーを１種単独で用いても、２種以上併用いてもよい。言い換えると、（Ｃ）エチレン・α－オレフィン共重合体は化石燃料由来のモノマーのみから構成されてもよいし、バイオマス由来のモノマーのみから構成されてもよいし、化石燃料由来のモノマーおよびバイオマス由来のモノマーを併用してよい。化石燃料とは、石油、石炭、天然ガス、シェールガス又はそれらの組合せである。バイオマスとは、菌類、酵母、藻類および細菌類を含む、植物由来または動物由来などの、あらゆる再生可能な天然原料およびその残渣である。 (C) The origin of the monomer used in the ethylene-α-olefin copolymer is not particularly limited. For example, a fossil fuel-derived monomer or a biomass-derived monomer can be used. They may be used, or two or more of them may be used in combination. In other words, (C) the ethylene/α-olefin copolymer may be composed only of a fossil fuel-derived monomer, may be composed only of a biomass-derived monomer, or may be composed of a fossil fuel-derived monomer and a biomass-derived monomer. may be used together. Fossil fuels are oil, coal, natural gas, shale gas, or combinations thereof. Biomass is any renewable natural raw material and its residues, such as of plant or animal origin, including fungi, yeasts, algae and bacteria.
　本発明における（Ｃ）エチレン－α－オレフィン共重合体の製造方法は特に限定されないが、特公平２－１１６３号公報、特公平２－７９９８号公報に記載されているようなバナジウム化合物と有機アルミニウム化合物とからなるバナジウム系触媒による方法が挙げられる。また、高い重合活性で共重合体を製造する方法として特開昭６１－２２１２０７号公報、特公平７－１２１９６９号公報、特許第２７９６３７６号公報に記載されているようなジルコノセンなどのメタロセン化合物と有機アルミニウムオキシ化合物（アルミノキサン）からなる触媒系を用いる方法等を用いてもよい。この方法は、得られる共重合体の塩素含量、およびプロピレンの２，１－挿入が低減できるため、より好ましい。バナジウム系触媒による方法では、メタロセン系触媒を用いる方法に対し、助触媒に塩素化合物をより多く使用するため、得られる（Ｃ）エチレン－α－オレフィン共重合体中に微量の塩素が残存する可能性がある。 The method for producing (C) the ethylene-α-olefin copolymer in the present invention is not particularly limited. and a method using a vanadium-based catalyst consisting of a compound. In addition, as a method for producing a copolymer with high polymerization activity, metallocene compounds such as zirconocene and organic A method using a catalyst system comprising an aluminum oxy compound (aluminoxane) may also be used. This method is more preferred because the chlorine content of the resulting copolymer and the 2,1-insertion of propylene can be reduced. Compared to the method using a metallocene catalyst, the method using a vanadium catalyst uses a greater amount of chlorine compounds in the co-catalyst, so a trace amount of chlorine may remain in the resulting ethylene-α-olefin copolymer (C). have a nature.
　一方、メタロセン系触媒を用いる方法では、実質的に塩素を残存させないため、機械等における金属部分の腐食の可能性を考慮する必要がなくなる。塩素含量は１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、２０ｐｐｍ以下であることがさらに好ましく、５ｐｐｍ以下であることが特に好ましい。塩素含量は種々の公知の方法で定量することができる。本発明における具体的な測定方法は実施例に記載した通りである。 On the other hand, in the method using a metallocene catalyst, virtually no chlorine remains, so there is no need to consider the possibility of corrosion of metal parts in machines. The chlorine content is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 20 ppm or less, and particularly preferably 5 ppm or less. Chlorine content can be determined by various known methods. A specific measuring method in the present invention is as described in Examples.
　また、プロピレンの２，１－挿入低減は、共重合体分子内のエチレン連鎖をより低減することが可能になり、エチレンの分子内結晶性を抑制できることから、潤滑油組成物の粘度温度特性、低温粘度特性を向上させることができる。 In addition, the 2,1-insertion reduction of propylene makes it possible to further reduce the ethylene chains in the copolymer molecule, and the intramolecular crystallinity of ethylene can be suppressed, so the viscosity temperature characteristics of the lubricating oil composition, Low temperature viscosity characteristics can be improved.
　特に以下のような方法を用いることにより、分子量制御、分子量分布、非晶性、Ｂ値の点において良好な性能バランスを有する（Ｃ）エチレン－α－オレフィン共重合体が得られる。 In particular, by using the following method, an ethylene-α-olefin copolymer (C) having a good performance balance in terms of molecular weight control, molecular weight distribution, amorphousness, and B value can be obtained.
　前記（Ｃ）エチレン－α－オレフィン共重合体は、下記一般式［Ｉ］で表される架橋メタロセン化合物（ａ）、ならびに、有機金属化合物（ｂ－１）、有機アルミニウムオキシ化合物（ｂ－２）および前記架橋メタロセン化合物（ａ）と反応してイオン対を形成する化合物（ｂ－３）からなる群より選ばれる少なくとも１種の化合物（ｂ）を含むオレフィン重合触媒の存在下で、エチレンと炭素数が３～２０のα－オレフィンとを共重合することにより製造することができる。 The (C) ethylene-α-olefin copolymer includes a bridged metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), and an organoaluminumoxy compound (b-2). ) and a compound (b-3) that forms an ion pair by reacting with the bridged metallocene compound (a) in the presence of an olefin polymerization catalyst containing ethylene and It can be produced by copolymerizing an α-olefin having 3 to 20 carbon atoms.
Figure JPOXMLDOC01-appb-C000005
 　＜架橋メタロセン化合物＞
　架橋メタロセン化合物（ａ）は、上記式［Ｉ］で表される。式［Ｉ］中のＹ、Ｍ、Ｒ1～Ｒ14、Ｑ、ｎおよびｊを以下に説明する。
Figure JPOXMLDOC01-appb-C000005
 <Bridged Metallocene Compound>
The bridged metallocene compound (a) is represented by the above formula [I]. Y, M, R 1 to R 14 , Q, n and j in formula [I] are explained below.
　（Ｙ、Ｍ、Ｒ1～Ｒ14、Ｑ、ｎおよびｊ）
　Ｙは、第１４族原子であり、例えば、炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子が挙げられ、好ましくは炭素原子またはケイ素原子であり、より好ましくは炭素原子である。 (Y, M, R 1 -R 14 , Q, n and j)
Y is a Group 14 atom, such as carbon atom, silicon atom, germanium atom and tin atom, preferably carbon atom or silicon atom, more preferably carbon atom.
　Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子であり、好ましくはジルコニウム原子である。 M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.
　Ｒ1～Ｒ12は、水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群より選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよい。また、Ｒ1からＲ12までの隣接した置換基は互いに結合して環を形成していてもよく、互いに結合していなくてもよい。 R 1 to R 12 are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; , may be the same or different. Adjacent substituents of R 1 to R 12 may or may not be bonded to each other to form a ring.
　ここで、炭素数１～２０の炭化水素基としては、炭素数１～２０のアルキル基、炭素数３～２０の環状飽和炭化水素基、炭素数２～２０の鎖状不飽和炭化水素基、炭素数３～２０の環状不飽和炭化水素基、炭素数１～２０のアルキレン基、炭素数６～２０のアリーレン基等が例示される。 Here, the hydrocarbon group having 1 to 20 carbon atoms includes an alkyl group having 1 to 20 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, Examples include a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like.
　炭素数１～２０のアルキル基としては、直鎖状飽和炭化水素基であるメチル基、エチル基、ｎ－プロピル基、アリル（ａｌｌｙｌ）基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デカニル基など、分岐状飽和炭化水素基であるイソプロピル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ｔ－アミル基、ネオペンチル基、３－メチルペンチル基、１，１－ジエチルプロピル基、１，１－ジメチルブチル基、１－メチル－１－プロピルブチル基、１，１－プロピルブチル基、１，１－ジメチル－２－メチルプロピル基、１－メチル－１－イソプロピル－２－メチルプロピル基、シクロプロピルメチル基などが例示される。アルキル基の炭素数は好ましくは１～６である。 Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group and n-hexyl. group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, branched saturated hydrocarbon group isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl -2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopropylmethyl group and the like. The number of carbon atoms in the alkyl group is preferably 1-6.
　炭素数３～２０の環状飽和炭化水素基としては、環状飽和炭化水素基であるシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルネニル基、１－アダマンチル基、２－アダマンチル基など、環状飽和炭化水素基の水素原子が炭素数１～１７の炭化水素基で置き換えられた基である３－メチルシクロペンチル基、３－メチルシクロヘキシル基、４－メチルシクロヘキシル基、４－シクロヘキシルシクロヘキシル基、４－フェニルシクロヘキシル基などが例示される。環状飽和炭化水素基の炭素数は好ましくは５～１１である。 Examples of the saturated cyclic hydrocarbon group having 3 to 20 carbon atoms include a saturated cyclic hydrocarbon group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4, which are groups in which the hydrogen atoms of a cyclic saturated hydrocarbon group are replaced with hydrocarbon groups having 1 to 17 carbon atoms, such as 2-adamantyl group -cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like. The cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.
　炭素数２～２０の鎖状不飽和炭化水素基としては、アルケニル基であるエテニル基（ビニル基）、１－プロペニル基、２－プロペニル基（アリル基）、１－メチルエテニル基（イソプロペニル基）など、アルキニル基であるエチニル基、１－プロピニル基、２－プロピニル基（プロパルギル基）などが例示される。鎖状不飽和炭化水素基の炭素数は好ましくは２～４である。 Examples of chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). and the like, which are alkynyl groups such as ethynyl group, 1-propynyl group and 2-propynyl group (propargyl group). The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.
　炭素数３～２０の環状不飽和炭化水素基としては、環状不飽和炭化水素基であるシクロペンタジエニル基、ノルボルニル基、フェニル基、ナフチル基、インデニル基、アズレニル基、フェナントリル基、アントラセニル基など、環状不飽和炭化水素基の水素原子が炭素数１～１５の炭化水素基で置き換えられた基である３－メチルフェニル基（ｍ－トリル基）、４－メチルフェニル基（ｐ－トリル基）、４－エチルフェニル基、４－ｔ－ブチルフェニル基、４－シクロヘキシルフェニル基、ビフェニリル基、３，４－ジメチルフェニル基、３，５－ジメチルフェニル基、２，４，６－トリメチルフェニル基（メシチル基）など、直鎖状炭化水素基または分岐状飽和炭化水素基の水素原子が炭素数３～１９の環状飽和炭化水素基または環状不飽和炭化水素基で置き換えられた基であるベンジル基、クミル基などが例示される。環状不飽和炭化水素基の炭素数は好ましくは６～１０である。 Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group. , 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which the hydrogen atom of a cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms , 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( a benzyl group, which is a group in which hydrogen atoms of a linear hydrocarbon group or branched saturated hydrocarbon group are replaced with a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms, such as a mesityl group; A cumyl group and the like are exemplified. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6-10.
　炭素数１～２０のアルキレン基としては、メチレン基、エチレン基、ジメチルメチレン基（イソプロピリデン基）、エチルメチレン基、メチルエチレン基、ｎ－プロピレン基などが例示される。アルキレン基の炭素数は好ましくは１～６である。 Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, methylethylene group, n-propylene group and the like. The alkylene group preferably has 1 to 6 carbon atoms.
　炭素数６～２０のアリーレン基としては、ｏ－フェニレン基、ｍ－フェニレン基、ｐ－フェニレン基、４，４'－ビフェニリレン基などが例示される。アリ－レン基の炭素数は好ましくは６～１２である。 Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group and 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.
　ケイ素含有基としては、炭素数１～２０の炭化水素基において、炭素原子がケイ素原子で置き換えられた基であるトリメチルシリル基、トリエチルシリル基、ｔ－ブチルジメチルシリル基、トリイソプロピルシリル基等のアルキルシリル基、ジメチルフェニルシリル基、メチルジフェニルシリル基、ｔ－ブチルジフェニルシリル基等のアリールシリル基、ペンタメチルジシラニル基、トリメチルシリルメチル基などが例示される。アルキルシリル基の炭素数は１～１０が好ましく、アリールシリル基の炭素数は６～１８が好ましい。 Examples of the silicon-containing group include alkyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group, which are hydrocarbon groups having 1 to 20 carbon atoms in which the carbon atoms are replaced with silicon atoms. Examples include a silyl group, an arylsilyl group such as a dimethylphenylsilyl group, a methyldiphenylsilyl group, a t-butyldiphenylsilyl group, a pentamethyldisilanyl group, and a trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.
　窒素含有基としては、アミノ基や、上述した炭素数１～２０の炭化水素基またはケイ素含有基において、＝ＣＨ－構造単位が窒素原子で置き換えられた基、－ＣＨ2-構造単位が炭素数１～２０の炭化水素基が結合した窒素原子で置き換えられた基、または－ＣＨ3構造単位が炭素数１～２０の炭化水素基が結合した窒素原子またはニトリル基で置き換えられた基であるジメチルアミノ基、ジエチルアミノ基、Ｎ－モルフォリニル基、ジメチルアミノメチル基、シアノ基、ピロリジニル基、ピペリジニル基、ピリジニル基など、Ｎ－モルフォリニル基およびニトロ基などが例示される。窒素含有基としては、ジメチルアミノ基、Ｎ－モルフォリニル基が好ましい。 Examples of the nitrogen-containing group include an amino group, a group in which the =CH- structural unit is replaced with a nitrogen atom in the above-described hydrocarbon group having 1 to 20 carbon atoms or silicon-containing group, and -CH 2 - structural unit having a carbon number. A group substituted with a nitrogen atom to which a hydrocarbon group of 1 to 20 is attached, or a group in which the —CH 3 structural unit is replaced by a nitrogen atom or a nitrile group to which a hydrocarbon group of 1 to 20 carbon atoms is attached, dimethyl Examples include amino group, diethylamino group, N-morpholinyl group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group, N-morpholinyl group and nitro group. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferred.
　酸素含有基としては、水酸基や、上述した炭素数１～２０の炭化水素基、ケイ素含有基または窒素含有基において、－ＣＨ2－構造単位が酸素原子またはカルボニル基で置き換えられた基、または－ＣＨ3構造単位が炭素数１～２０の炭化水素基が結合した酸素原子で置き換えられた基であるメトキシ基、エトキシ基、ｔ－ブトキシ基、フェノキシ基、トリメチルシロキシ基、メトキシエトキシ基、ヒドロキシメチル基、メトキシメチル基、エトキシメチル基、ｔ－ブトキシメチル基、１－ヒドロキシエチル基、１－メトキシエチル基、１－エトキシエチル基、２－ヒドロキシエチル基、２－メトキシエチル基、２－エトキシエチル基、ｎ－２－オキサブチレン基、ｎ－２－オキサペンチレン基、ｎ－３－オキサペンチレン基、アルデヒド基、アセチル基、プロピオニル基、ベンゾイル基、トリメチルシリルカルボニル基、カルバモイル基、メチルアミノカルボニル基、カルボキシ基、メトキシカルボニル基、カルボキシメチル基、エトカルボキシメチル基、カルバモイルメチル基、フラニル基、ピラニル基などが例示される。酸素含有基としては、メトキシ基が好ましい。 The oxygen-containing group includes a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group in which the —CH 2 — structural unit is replaced with an oxygen atom or a carbonyl group, or — Methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl, which is a group in which the CH 3 structural unit is replaced by an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, pyranyl group and the like. A methoxy group is preferred as the oxygen-containing group.
　ハロゲン原子としては、第１７族元素であるフッ素、塩素、臭素、ヨウ素などが例示される。ハロゲン含有基としては、上述した炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基または酸素含有基において、水素原子がハロゲン原子によって置換された基であるトリフルオロメチル基、トリブロモメチル基、ペンタフルオロエチル基、ペンタフルオロフェニル基などが例示される。 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, which are Group 17 elements. Examples of the halogen-containing group include a trifluoromethyl group and a tribromo group, which are groups in which hydrogen atoms are substituted by halogen atoms in the above-mentioned hydrocarbon group, silicon-containing group, nitrogen-containing group or oxygen-containing group having 1 to 20 carbon atoms. Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.
　Ｑは、ハロゲン原子、炭素数１～２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から、同一のまたは異なる組合せで選ばれる。ハロゲン原子および炭素数１～２０の炭化水素基の詳細は、上述のとおりである。Ｑがハロゲン原子である場合は、塩素原子が好ましい。Ｑが炭素数１～２０の炭化水素基である場合は、該炭化水素基の炭素数は１～７であることが好ましい。 Q is selected in the same or different combination from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands and neutral ligands capable of coordinating with lone electron pairs. The details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. A chlorine atom is preferred when Q is a halogen atom. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.
　アニオン配位子としては、メトキシ基、ｔ－ブトキシ基、フェノキシ基などのアルコキシ基、アセテート、ベンゾエートなどのカルボキシレート基、メシレート、トシレートなどのスルホネート基などを例示することができる。 Examples of anionic ligands include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.
　孤立電子対で配位可能な中性配位子としては、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニルメチルホスフィンなどの有機リン化合物、テトラヒドロフラン、ジエチルエーテル、ジオキサン、１，２－ジメトキシエタンなどのエーテル化合物などを例示することができる。 Neutral ligands capable of coordinating with a lone pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like. Ether compounds and the like can be exemplified.
　ｊは１～４の整数であり、好ましくは２である。 j is an integer of 1 to 4, preferably 2;
　ｎは１～４の整数であり、好ましくは１または２であり、さらに好ましくは１である。 n is an integer of 1 to 4, preferably 1 or 2, more preferably 1.
　Ｒ13およびＲ14は水素原子、炭素数１～２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群より選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよい。また、Ｒ13およびＲ14は互いに結合して環を形成していてもよく、互いに結合していなくてもよい。 R 13 and R 14 are selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; atoms or substituents, each of which may be the same or different. Also, R 13 and R 14 may be bonded to each other to form a ring, or may not be bonded to each other.
　炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基の詳細については、上述の通りである。 The details of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom and the halogen-containing group are as described above.
　アリール基としては、前述した炭素数３～２０の環状不飽和炭化水素基の例と一部重複するが、芳香族化合物から誘導された置換基であるフェニル基、１－ナフチル基、２－ナフチル基、アントラセニル基、フェナントレニル基、テトラセニル基、クリセニル基、ピレニル基、インデニル基、アズレニル基、ピロリル基、ピリジル基、フラニル基、チオフェニル基などが例示される。アリール基としては、フェニル基または２－ナフチル基が好ましい。 The aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms described above, but is a substituent derived from an aromatic compound, namely a phenyl group, a 1-naphthyl group and a 2-naphthyl group. group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like. As the aryl group, a phenyl group or a 2-naphthyl group is preferred.
　前記芳香族化合物としては、芳香族炭化水素および複素環式芳香族化合物であるベンゼン、ナフタレン、アントラセン、フェナントレン、テトラセン、クリセン、ピレン、インデン、アズレン、ピロール、ピリジン、フラン、チオフェンなどが例示される。 Examples of the aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene. .
　置換アリール基としては、前述した炭素数３～２０の環状不飽和炭化水素基の例と一部重複するが、前記アリール基が有する１以上の水素原子が炭素数１～２０の炭化水素基、アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群より選ばれる少なくとも１種の置換基により置換されてなる基が挙げられ、具体的には３－メチルフェニル基（ｍ－トリル基）、４－メチルフェニル基（ｐ－トリル基）、３－エチルフェニル基、４－エチルフェニル基、３，４－ジメチルフェニル基、３，５－ジメチルフェニル基、ビフェニリル基、４－（トリメチルシリル）フェニル基、４－アミノフェニル基、４－（ジメチルアミノ）フェニル基、４－（ジエチルアミノ）フェニル基、４－モルフォリニルフェニル基、４－メトキシフェニル基、４－エトキシフェニル基、４－フェノキシフェニル基、３，４－ジメトキシフェニル基、３，５－ジメトキシフェニル基、３－メチル－４－メトキシフェニル基、３，５－ジメチル－４－メトキシフェニル基、３－（トリフルオロメチル）フェニル基、４－（トリフルオロメチル）フェニル基、３－クロロフェニル基、４－クロロフェニル基、３－フルオロフェニル基、４－フルオロフェニル基、５－メチルナフチル基、２－（６－メチル）ピリジル基などが例示される。 The substituted aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but at least one hydrogen atom of the aryl group is a hydrocarbon group having 1 to 20 carbon atoms, A group substituted with at least one substituent selected from the group consisting of an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, specifically 3-methyl phenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4-(trimethylsilyl)phenyl group, 4-aminophenyl group, 4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxy Phenyl group, 4-phenoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3-( trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2-(6- methyl)pyridyl group and the like are exemplified.
　上記式［Ｉ］で表される架橋メタロセン化合物（ａ）において、ｎは１であることが好ましい。このような架橋メタロセン化合物（以下「架橋メタロセン化合物（ａ－１）」ともいう。）は、下記一般式［ＩＩ］で表わされる。 In the bridged metallocene compound (a) represented by formula [I] above, n is preferably 1. Such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-1)”) is represented by the following general formula [II].
Figure JPOXMLDOC01-appb-C000006
 　式［ＩＩ］において、Ｙ、Ｍ、Ｒ1～Ｒ14、Ｑおよびｊの定義等は、上述のとおりである。
Figure JPOXMLDOC01-appb-C000006
 In formula [II], the definitions of Y, M, R 1 to R 14 , Q and j are as described above.
　架橋メタロセン化合物（ａ－１）は、上記式［Ｉ］におけるｎが２～４の整数である化合物に比べ、製造工程が簡素化され、製造コストが低減され、ひいてはこの架橋メタロセン化合物（ａ－１）を用いることで（Ｃ）エチレン－α－オレフィン共重合体の製造コストが低減されるという利点が得られる。 The bridged metallocene compound (a-1) has a simpler production process and a lower production cost than the compound in which n is an integer of 2 to 4 in the above formula [I]. The use of 1) provides the advantage of reducing the production cost of (C) the ethylene-α-olefin copolymer.
　上記式［ＩＩ］で表される架橋メタロセン化合物（ａ－１）において、Ｒ1、Ｒ2、Ｒ3およびＲ4は全て水素であることが好ましい。このような架橋メタロセン化合物（以下「架橋メタロセン化合物（ａ－２）」ともいう。）は、下記一般式［ＩＩＩ］で表わされる。 In the bridged metallocene compound (a-1) represented by the above formula [II], R 1 , R 2 , R 3 and R 4 are all preferably hydrogen. Such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-2)”) is represented by the following general formula [III].
Figure JPOXMLDOC01-appb-C000007
 　式［ＩＩＩ］において、Ｙ、Ｍ、Ｒ5～Ｒ14、Ｑおよびｊの定義等は、上述のとおりである。
Figure JPOXMLDOC01-appb-C000007
 In formula [III], the definitions of Y, M, R 5 to R 14 , Q and j are as described above.
　架橋メタロセン化合物（ａ－２）は、上記式［Ｉ］におけるＲ1、Ｒ2、Ｒ3およびＲ4のいずれか一つ以上が水素原子以外の置換基で置換された化合物に比べ、製造工程が簡素化され、製造コストが低減され、ひいてはこの架橋メタロセン化合物（ａ－２）を用いることで（Ｃ）エチレン－α－オレフィン共重合体の製造コストが低減されるという利点が得られる。また、一般に高温重合を行うことにより、（Ｃ）エチレン－α－オレフィン共重合体のランダム性は低下することが知られているが、該架橋メタロセン化合物（ａ－２）を含むオレフィン重合触媒の存在下でエチレンと炭素数３～２０のα－オレフィンから選ばれる１種以上のモノマーとを共重合する場合、高温重合であっても、得られる（Ｃ）エチレン－α－オレフィン共重合体のランダム性が高いという利点も得られる。 The bridged metallocene compound (a-2) has a lower manufacturing process than a compound in which one or more of R 1 , R 2 , R 3 and R 4 in the above formula [I] is substituted with a substituent other than a hydrogen atom. is simplified, the production cost is reduced, and the use of the crosslinked metallocene compound (a-2) further reduces the production cost of the ethylene-α-olefin copolymer (C). Further, it is generally known that the randomness of (C) an ethylene-α-olefin copolymer is reduced by carrying out high-temperature polymerization. When ethylene and one or more monomers selected from α-olefins having 3 to 20 carbon atoms are copolymerized in the presence of the It also has the advantage of being highly random.
　上記式［ＩＩＩ］で表される架橋メタロセン化合物（ａ－２）において、Ｒ13およびＲ14のいずれか一方が、アリール基または置換アリール基であることが好ましい。このような架橋メタロセン化合物（ａ－３）は、Ｒ13およびＲ14がいずれもアリール基および置換アリール基以外の置換基である場合に比べ、生成する（Ｃ）エチレン－α－オレフィン共重合体中の二重結合量が少ないという利点が得られる。 In the bridged metallocene compound (a-2) represented by formula [III], either one of R 13 and R 14 is preferably an aryl group or a substituted aryl group. Such a bridged metallocene compound (a-3) produces (C) an ethylene-α-olefin copolymer as compared with the case where both R 13 and R 14 are substituents other than an aryl group and a substituted aryl group. An advantage is obtained that the amount of double bonds in the medium is small.
　架橋メタロセン化合物（ａ－３）において、Ｒ13およびＲ14のいずれか一方が、アリール基または置換アリール基であり、他方が炭素数１～２０のアルキル基であることがさらに好ましく、Ｒ13およびＲ14のいずれか一方が、アリール基または置換アリール基であり、他方がメチル基であることが特に好ましい。このような架橋メタロセン化合物（以下「架橋メタロセン化合物（ａ－４）」ともいう。）は、Ｒ13およびＲ14がいずれもアリール基または置換アリール基である場合に比べ、生成する（Ｃ）エチレン－α－オレフィン共重合体中の二重結合量と重合活性とのバランスに優れ、この架橋メタロセン化合物を用いることで（Ｃ）エチレン－α－オレフィン共重合体の製造コストが低減されるという利点が得られる。 In the bridged metallocene compound (a-3), one of R 13 and R 14 is more preferably an aryl group or a substituted aryl group, and the other is an alkyl group having 1 to 20 carbon atoms. It is particularly preferred that either one of R 14 is an aryl group or substituted aryl group and the other is a methyl group. In such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a- 4 )” ) , the produced (C) ethylene - An advantage that the balance between the amount of double bonds in the α-olefin copolymer and the polymerization activity is excellent, and the production cost of the (C) ethylene-α-olefin copolymer is reduced by using this crosslinked metallocene compound. is obtained.
　ある一定の重合器内全圧および温度の条件下で重合を実施する場合において、水素導入による水素分圧の上昇は重合モノマーであるオレフィンの分圧の低下を引き起こし、とりわけ水素分圧が高い領域において重合速度を低下させるという問題を生じる。重合反応器はその設計上許容される内部全圧が制限されているため、特に低分子量のオレフィン重合体を製造する際に過度な水素導入を必要とすると、オレフィン分圧が著しく低下するため、重合活性が低下する場合がある。しかしながら、架橋メタロセン化合物（ａ－４）を用いて本発明における（Ｃ）エチレン－α－オレフィン共重合体を製造する場合、上記架橋メタロセン化合物（ａ－３）を用いる場合に比べ、重合反応器に導入する水素量が低減され、重合活性が向上し、（Ｃ）エチレン－α－オレフィン共重合体の製造コストが低減されるという利点が得られる。 When the polymerization is carried out under the conditions of a certain total pressure and temperature in the polymerization vessel, the increase in the hydrogen partial pressure due to the introduction of hydrogen causes a decrease in the partial pressure of the olefin, which is the polymerization monomer, especially in the region where the hydrogen partial pressure is high. causes a problem of slowing down the polymerization rate. Since the polymerization reactor has a limited internal total pressure due to its design, if excessive hydrogen introduction is required especially when producing a low-molecular-weight olefin polymer, the olefin partial pressure will drop significantly. Polymerization activity may decrease. However, when producing the (C) ethylene-α-olefin copolymer of the present invention using the crosslinked metallocene compound (a-4), the polymerization reactor is more The amount of hydrogen introduced into is reduced, the polymerization activity is improved, and the production cost of (C) the ethylene-α-olefin copolymer is reduced.
　上記架橋メタロセン化合物（ａ－４）において、Ｒ6およびＲ11は隣接した置換基と互いに結合して環を形成していてもよい、炭素数１～２０のアルキル基または炭素数１～２０のアルキレン基であることが好ましい。このような架橋メタロセン化合物（以下「架橋メタロセン化合物（ａ－５）」ともいう。）は、Ｒ6およびＲ11が炭素数１～２０のアルキル基または炭素数１～２０のアルキレン基以外の置換基で置換された化合物に比べ、製造工程が簡素化され、製造コストが低減され、ひいてはこの架橋メタロセン化合物（ａ－５）を用いることで（Ｃ）エチレン－α－オレフィン共重合体の製造コストが低減されるという利点が得られる。 In the bridged metallocene compound (a-4), R 6 and R 11 are alkyl groups having 1 to 20 carbon atoms or An alkylene group is preferred. Such a bridged metallocene compound ( hereinafter also referred to as “bridged metallocene compound (a-5)”) has a substituted Compared to a compound substituted with a group, the production process is simplified, the production cost is reduced, and the production cost of the (C) ethylene-α-olefin copolymer is reduced by using this crosslinked metallocene compound (a-5). has the advantage of being reduced.
　上記一般式［Ｉ］で表される架橋メタロセン化合物（ａ）、上記一般式［ＩＩ］で表される架橋メタロセン化合物（ａ－１）、上記一般式［ＩＩＩ］で表される架橋メタロセン化合物（ａ－２）、ならびに上記架橋メタロセン化合物（ａ－３）、（ａ－４）および（ａ－５）において、Ｍはジルコニウム原子であることがさらに好ましい。Ｍがジルコニウム原子である上記架橋メタロセン化合物を含むオレフィン重合触媒の存在下でエチレンと炭素数３～２０のα－オレフィンから選ばれる１種以上のモノマーとを共重合する場合、Ｍがチタン原子またはハフニウム原子である場合に比べ重合活性が高く、（Ｃ）エチレン－α－オレフィン共重合体の製造コストが低減されるという利点が得られる。 The bridged metallocene compound (a) represented by the general formula [I], the bridged metallocene compound (a-1) represented by the general formula [II], the bridged metallocene compound represented by the general formula [III] ( In a-2) and the above bridged metallocene compounds (a-3), (a-4) and (a-5), M is more preferably a zirconium atom. When copolymerizing ethylene and one or more monomers selected from α-olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing the above-mentioned crosslinked metallocene compound in which M is a zirconium atom, M is a titanium atom or As compared with hafnium atoms, the polymerization activity is higher, and the production cost of (C) the ethylene-α-olefin copolymer is reduced.
　このような架橋メタロセン化合物（ａ）としては、
　［ジメチルメチレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［ジメチルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジメチルメチレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジメチルメチレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［ジメチルメチレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［シクロヘキシリデン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［シクロヘキシリデン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［シクロヘキシリデン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［シクロヘキシリデン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［シクロヘキシリデン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［ジフェニルメチレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［ジフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、ジフェニルメチレン（η5－２－メチル－４－ｔ－ブチルシクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジフェニルメチレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジフェニルメチレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、ジフェニルメチレン｛η5－（２－メチル－４－ｉ－プロピルシクロペンタジエニル）｝（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［ジフェニルメチレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［メチル（３－メチルフェニル）メチレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［メチル（３－メチルフェニル）メチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［メチル（３－メチルフェニル）メチレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［メチル（３－メチルフェニル）メチレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［メチル（３－メチルフェニル）メチレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［ジフェニルシリレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［ジフェニルシリレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジフェニルシリレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジフェニルシリレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［ジフェニルシリレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［ビス（３－メチルフェニル）シリレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［ビス（３－メチルフェニル）シリレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ビス（３－メチルフェニル）シリレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ビス（３－メチルフェニル）シリレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［ビス（３－メチルフェニル）シリレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［ジシクロヘキシルシリレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［ジシクロヘキシルシリレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジシクロヘキシルシリレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［ジシクロヘキシルシリレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［ジシクロヘキシルシリレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、
　［エチレン（η5－シクロペンタジエニル）（η5－フルオレニル）］ジルコニウムジクロリド、［エチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［エチレン（η5－シクロペンタジエニル）（η5－３，６－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド、［エチレン（η5－シクロペンタジエニル）（η5－オクタメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、［エチレン（η5－シクロペンタジエニル）（η5－テトラメチルオクタヒドロジベンゾフルオレニル）］ジルコニウムジクロリド、等が挙げられる。 As such a bridged metallocene compound (a),
[dimethylmethylene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)]zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl )]zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl)(η 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl) (η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,
[Cyclohexylidene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)]zirconium dichloride, [Cyclohexylidene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluoro olenyl)]zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [cyclohexylidene (η 5 -cyclo pentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [cyclohexylidene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride ,
[diphenylmethylene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)] zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl) (η 5-2,7-di-t-butylfluorenyl) ]zirconium dichloride, diphenylmethylene (η 5 -2-methyl-4-t-butylcyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl)(η 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluor olenyl)]zirconium dichloride, diphenylmethylene {η 5 -(2-methyl-4-i-propylcyclopentadienyl)}(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylmethylene ( η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,
[methylphenylmethylene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)]zirconium dichloride, [methylphenylmethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluoro olenyl)]zirconium dichloride, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene (η 5 -cyclo pentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methylphenylmethylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride ,
[methyl (3-methylphenyl) methylene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)] zirconium dichloride, [methyl (3-methylphenyl) methylene (η 5 -cyclopentadienyl) (η 5 - 2,7-di-t-butylfluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -3,6-di-t-butylfluorenyl) nil)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,
[diphenylsilylene (η 5 -cyclopentadienyl) (η5-fluorenyl)]zirconium dichloride, [diphenylsilylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl) ] zirconium dichloride, [diphenylsilylene (η 5 -cyclopentadienyl) (η 5 -3,6-di-t-butylfluorenyl)] zirconium dichloride, [diphenylsilylene (η 5 -cyclopentadienyl) ( η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylsilylene (η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,
[bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -fluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 - 2,7-di-t-butylfluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene (η 5 -cyclopentadienyl)(η 5 -3,6-di-t-butylfluorenyl) nil)]zirconium dichloride, [bis(3-methylphenyl)silylene (η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene (η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,
[Dicyclohexylsilylene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)]zirconium dichloride, [Dicyclohexylsilylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl )] zirconium dichloride, [dicyclohexylsilylene (η 5 -cyclopentadienyl) (η 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [dicyclohexylsilylene (η 5 -cyclopentadienyl) (η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dicyclohexylsilylene (η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,
[ethylene (η 5 -cyclopentadienyl) (η 5 -fluorenyl)]zirconium dichloride, [ethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl)] Zirconium dichloride, [ethylene (η 5 -cyclopentadienyl) (η 5 -3,6-di-t-butylfluorenyl)]zirconium dichloride, [ethylene (η 5 -cyclopentadienyl) (η 5 - octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [ethylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride, and the like.
　これらの化合物のジルコニウム原子をハフニウム原子に置き換えた化合物またはクロロ配位子をメチル基に置き換えた化合物などが例示されるが、架橋メタロセン化合物（ａ）はこれらの例示に限定されない。尚、例示した架橋メタロセン化合物（ａ）の構成部分であるη5－テトラメチルオクタヒドロジベンゾフルオレニルは４，４，７，７－テトラメチル－（５ａ，５ｂ，１１ａ，１２，１２ａ－η5）－１，２，３，４，７，８，９，１０－オクタヒドロジベンゾ［ｂ，Ｈ］フルオレニル基、η5－オクタメチルオクタヒドロジベンゾフルオレニルは１，１，４，４，７，７，１０，１０－オクタメチル－（５ａ，５ｂ，１１ａ，１２，１２ａ－η5）－１，２，３，４，７，８，９，１０－オクタヒドロジベンゾ［ｂ，Ｈ］フルオレニル基をそれぞれ表わす。 Compounds in which the zirconium atom of these compounds is replaced with a hafnium atom or compounds in which the chloro ligand is replaced with a methyl group are exemplified, but the bridged metallocene compound (a) is not limited to these exemplifications. η 5 -tetramethyloctahydrodibenzofluorenyl, which is a constituent part of the exemplified bridged metallocene compound (a), is 4,4,7,7-tetramethyl-(5a,5b,11a,12,12a-η 5 ) -1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl group, η 5 -octamethyloctahydrodibenzofluorenyl is 1,1,4,4, 7,7,10,10-octamethyl-(5a,5b,11a,12,12a-η 5 )-1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl each represents a group.
　＜化合物（ｂ）＞
　前記オレフィン重合触媒は、上記の架橋メタロセン化合物（ａ）、ならびに有機金属化合物（ｂ－１）、有機アルミニウムオキシ化合物（ｂ－２）および架橋メタロセン化合物（ａ）と反応してイオン対を形成する化合物（ｂ－３）からなる群より選ばれる少なくとも１種の化合物（ｂ）を含む。 <Compound (b)>
The olefin polymerization catalyst reacts with the bridged metallocene compound (a), the organometallic compound (b-1), the organoaluminum oxy compound (b-2) and the bridged metallocene compound (a) to form an ion pair. It contains at least one compound (b) selected from the group consisting of compounds (b-3).
　有機金属化合物（ｂ－１）として、具体的には下記のような周期表第１、２族および第１２、１３族の有機金属化合物が用いられる。 As the organometallic compound (b-1), specifically, the following organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table are used.
　（ｂ－１ａ）一般式　Ｒa mＡｌ（ＯＲb）nＨpＸq（式中、ＲaおよびＲbは、互いに同一でも異なっていてもよく、炭素数１～１５、好ましくは１～４の炭化水素基を示し、Ｘはハロゲン原子を示し、ｍは０＜ｍ≦３、ｎは０≦ｎ＜３、ｐは０≦ｐ＜３、ｑは０≦ｑ＜３の数であり、かつｍ＋ｎ＋ｐ＋ｑ＝３である）で表される有機アルミニウム化合物。 (b-1a) general formula R a m Al(OR b ) n H p X q (wherein R a and R b may be the same or different and have 1 to 15 carbon atoms, preferably 1 to 4, X is a halogen atom, m is 0<m≦3, n is 0≦n<3, p is 0≦p<3, and q is 0≦q<3. , and m+n+p+q=3).
　このような化合物として、
　トリメチルアルミニウム、トリエチルアルミニウム、トリ－ｎ－ブチルアルミニウム、トリ－ｎ－ヘキシルアルミニウム、トリ－ｎ－オクチルアルミニウムなどのトリ－ｎ－アルキルアルミニウム、
　トリイソプロピルアルミニウム、トリイソブチルアルミニウム、トリseｃ－ブチルアルミニウム、トリ－ｔ－ブチルアルミニウム、トリ－２－メチルブチルアルミニウム、トリ－３－メチルヘキシルアルミニウム、トリ－２－エチルヘキシルアルミニウムなどのトリ分岐状アルキルアルミニウム、
　トリシクロヘキシルアルミニウム、トリシクロオクチルアルミニウムなどのトリシクロアルキルアルミニウム、
　トリフェニルアルミニウム、トリ（４－メチルフェニル）アルミニウムなどのトリアリールアルミニウム、
　ジイソプロピルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライドなどのジアルキルアルミニウムハイドライド、
　一般式（i－Ｃ4Ｈ9）xＡｌy（Ｃ5Ｈ10）z（式中、ｘ、ｙ、ｚは正の数であり、ｚ≦２ｘである。）で表されるイソプレニルアルミニウムなどのアルケニルアルミニウム、
　イソブチルアルミニウムメトキシド、イソブチルアルミニウムエトキシドなどのアルキルアルミニウムアルコキシド、
　ジメチルアルミニウムメトキシド、ジエチルアルミニウムエトキシド、ジブチルアルミニウムブトキシドなどのジアルキルアルミニウムアルコキシド、
　エチルアルミニウムセスキエトキシド、ブチルアルミニウムセスキブトキシドなどのアルキルアルミニウムセスキアルコキシド、
　一般式Ｒa 2.5Ａｌ（ＯＲb）0.5などで表される平均組成を有する部分的にアルコキシ化されたアルキルアルミニウム、ジエチルアルミニウムフェノキシド、ジエチルアルミニウム（２，６－ジ－ｔ－ブチル－４－メチルフェノキシド）などのアルキルアルミニウムアリーロキシド、
　ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジブチルアルミニウムクロリド、ジエチルアルミニウムブロミド、ジイソブチルアルミニウムクロリドなどのジアルキルアルミニウムハライド、
　エチルアルミニウムセスキクロリド、ブチルアルミニウムセスキクロリド、エチルアルミニウムセスキブロミドなどのアルキルアルミニウムセスキハライド、
　エチルアルミニウムジクロリドなどのアルキルアルミニウムジハライドなどの部分的にハロゲン化されたアルキルアルミニウム、
　ジエチルアルミニウムヒドリド、ジブチルアルミニウムヒドリドなどのジアルキルアルミニウムヒドリド、
　エチルアルミニウムジヒドリド、プロピルアルミニウムジヒドリドなどのアルキルアルミニウムジヒドリドおよびその他の部分的に水素化されたアルキルアルミニウム、
　エチルアルミニウムエトキシクロリド、ブチルアルミニウムブトキシクロリド、エチルアルミニウムエトキシブロミドなどの部分的にアルコキシ化およびハロゲン化されたアルキルアルミニウム
などを例示することができる。また、上記一般式Ｒa mＡｌ（ＯＲb）nＨpＸqで表される化合物に類似する化合物も使用することができ、例えば窒素原子を介して２以上のアルミニウム化合物が結合した有機アルミニウム化合物を挙げることができる。このような化合物として具体的には、（Ｃ2Ｈ5）2ＡｌＮ（Ｃ2Ｈ5）Ａｌ（Ｃ2Ｈ5）2などを挙げることができる。 As such compounds,
tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum;
Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum ,
tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
triarylaluminum such as triphenylaluminum, tri(4-methylphenyl)aluminum,
dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride;
Isoprenyl aluminum represented by the general formula (iC 4 H 9 ) x Aly (C 5 H 10 ) z (wherein x, y and z are positive numbers and z≦2x) alkenyl aluminum, such as
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide,
Partially alkoxylated aluminum alkyls, diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide) having an average composition represented by the general formula R a 2.5 Al(ORb) 0.5 , etc. ), such as alkylaluminum aryloxides,
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and other partially hydrogenated alkylaluminums,
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide can be exemplified. Compounds similar to the compounds represented by the above general formula R am Al (OR b ) n H p X q can also be used, for example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. compounds can be mentioned. Specific examples of such compounds include (C 2 H 5 ) 2 AlN(C 2 H 5 )Al(C 2 H 5 ) 2 and the like.
　（ｂ－１ｂ）一般式　Ｍ2ＡｌＲa 4（式中、Ｍ2はＬｉ、ＮａまたはＫを示し、Ｒaは炭素数１～１５、好ましくは１～４の炭化水素基を示す。）で表される周期表第１族金属とアルミニウムとの錯アルキル化物。 (b-1b) of the general formula M 2 AlR a 4 (wherein M 2 represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms); A complex alkylate of a Group 1 metal of the periodic table and aluminum represented.
　このような化合物として、ＬｉＡｌ（Ｃ2Ｈ5）4、ＬｉＡｌ（Ｃ7Ｈ15）4などを例示することができる。 Examples of such compounds include LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 .
　（ｂ－１ｃ）一般式　ＲaＲbＭ3（式中、ＲaおよびＲbは、互いに同一でも異なっていてもよく、炭素数１～１５、好ましくは１～４の炭化水素基を示し、Ｍ3はＭｇ、ＺｎまたはＣｄである。）で表される周期表第２族または第１２族金属のジアルキル化合物。 (b-1c) general formula R a R b M 3 (wherein R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; , M 3 is Mg, Zn or Cd).
　有機アルミニウムオキシ化合物（ｂ－２）としては、従来公知のアルミノキサンをそのまま使用することができる。具体的には、下記一般式［ＩＶ］で表わされる化合物および下記一般式［Ｖ］で表わされる化合物を挙げることができる。 As the organoaluminumoxy compound (b-2), conventionally known aluminoxanes can be used as they are. Specifically, compounds represented by the following general formula [IV] and compounds represented by the following general formula [V] can be mentioned.
Figure JPOXMLDOC01-appb-C000008
 　式［ＩＶ］および［Ｖ］中、Ｒは炭素数１～１０の炭化水素基、ｎは２以上の整数を示す。
Figure JPOXMLDOC01-appb-C000008
 In formulas [IV] and [V], R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.
　特にＲがメチル基であるメチルアルミノキサンであってｎが３以上、好ましくは１０以上のものが利用される。これらアルミノキサン類に若干の有機アルミニウム化合物が混入していても差し支えない。 In particular, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with a small amount of organoaluminum compounds.
　本発明においてエチレンと炭素数が３以上のα－オレフィンとの共重合を高温で行う場合には、特開平２－７８６８７号公報に例示されているようなベンゼン不溶性の有機アルミニウムオキシ化合物も適用することができる。また、特開平２－１６７３０５号公報に記載されている有機アルミニウムオキシ化合物、特開平２－２４７０１号公報、特開平３－１０３４０７号公報に記載されている二種類以上のアルキル基を有するアルミノキサンなども好適に利用できる。なお、本発明で用いられることのある「ベンゼン不溶性の有機アルミニウムオキシ化合物」とは、６０℃のベンゼンに溶解するＡｌ成分がＡｌ原子換算で通常１０％以下、好ましくは５％以下、特に好ましくは２％以下であり、ベンゼンに対して不溶性または難溶性である化合物である。 In the present invention, when the copolymerization of ethylene and an α-olefin having 3 or more carbon atoms is carried out at a high temperature, a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687 is also applied. be able to. In addition, organic aluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more types of alkyl groups described in JP-A-2-24701 and JP-A-3-103407, etc. It can be used conveniently. The "benzene-insoluble organoaluminumoxy compound" that may be used in the present invention means that the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, particularly preferably 5% or less, in terms of Al atoms. It is a compound that is 2% or less and is insoluble or sparingly soluble in benzene.
　また、有機アルミニウムオキシ化合物（ｂ－２）として、下記一般式［ＶＩ］で表されるような修飾メチルアルミノキサン等も挙げることができる。 Further, examples of the organoaluminumoxy compound (b-2) include modified methylaluminoxane represented by the following general formula [VI].
Figure JPOXMLDOC01-appb-C000009
 　式［ＶＩ］中、Ｒは炭素数１～１０の炭化水素基、ｍおよびｎはそれぞれ独立に２以上の整数を示す。
Figure JPOXMLDOC01-appb-C000009
 In formula [VI], R is a hydrocarbon group having 1 to 10 carbon atoms, m and n each independently represent an integer of 2 or more.
　この修飾メチルアルミノキサンはトリメチルアルミニウムとトリメチルアルミニウム以外のアルキルアルミニウムを用いて調製されるものである。このような化合物は一般にＭＭＡＯと呼ばれている。このようなＭＭＡＯは米国特許４９６０８７８号公報および米国特許５０４１５８４号公報で挙げられている方法で調製することができる。また、東ソー・ファインケム社等からもトリメチルアルミニウムとトリイソブチルアルミニウムを用いて調製した、Ｒがイソブチル基であるものがＭＭＡＯやＴＭＡＯといった名称で市販されている。このようなＭＭＡＯは各種溶媒への溶解性および保存安定性を改良したアルミノキサンであり、具体的には上記式［ＩＶ］で表わされる化合物および［Ｖ］で表わされる化合物のうちのベンゼンに対して不溶性または難溶性の化合物とは違い、脂肪族炭化水素や脂環族炭化水素に溶解する。 This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by methods set forth in US Pat. Nos. 4,960,878 and 5,041,584. In addition, Tosoh Finechem Co., Ltd. and the like also sell products prepared using trimethylaluminum and triisobutylaluminum under the names of MMAO and TMAO, in which R is an isobutyl group. Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, among the compounds represented by the above formula [IV] and [V], Unlike insoluble or sparingly soluble compounds, it dissolves in aliphatic and alicyclic hydrocarbons.
　さらに、有機アルミニウムオキシ化合物（ｂ－２）として、下記一般式［ＶＩＩ］で表されるボロンを含んだ有機アルミニウムオキシ化合物も挙げることができる。 Furthermore, as the organoaluminumoxy compound (b-2), an organoaluminumoxy compound containing boron represented by the following general formula [VII] can also be mentioned.
Figure JPOXMLDOC01-appb-C000010
 　式［ＶＩＩ］中、Ｒcは炭素数１～１０の炭化水素基を示す。Ｒdは、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子または炭素数１～１０の炭化水素基を示す。
Figure JPOXMLDOC01-appb-C000010
 In formula [VII], R c represents a hydrocarbon group having 1 to 10 carbon atoms. R d may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
　架橋メタロセン化合物（ａ）と反応してイオン対を形成する化合物（ｂ－３）（以下、「イオン化イオン性化合物」または単に「イオン性化合物」と略称する場合がある。）としては、特表平１－５０１９５０号公報、特表平１－５０２０３６号公報、特開平３－１７９００５号公報、特開平３－１７９００６号公報、特開平３－２０７７０３号公報、特開平３－２０７７０４号公報、米国特許５３２１１０６号公報などに記載されたルイス酸、イオン性化合物、ボラン化合物およびカルボラン化合物などを挙げることができる。さらに、ヘテロポリ化合物およびイソポリ化合物も挙げることができる。 The compound (b-3) that reacts with the bridged metallocene compound (a) to form an ion pair (hereinafter sometimes abbreviated as "ionized ionic compound" or simply "ionic compound") is JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Patent Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-5321106. In addition, heteropolycompounds and isopolycompounds may also be mentioned.
　本発明において好ましく使用されるイオン化イオン性化合物は、下記一般式［ＶＩＩＩ］で表されるホウ素化合物である。 The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VIII].
Figure JPOXMLDOC01-appb-C000011
 　式［ＶＩＩＩ］中、Ｒe+としては、Ｈ+、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒf～Ｒiは、互いに同一でも異なっていてもよく、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、好ましくは置換アリール基である。
Figure JPOXMLDOC01-appb-C000011
 In formula [VIII], R e+ includes H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R f to R i may be the same or different, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. , preferably a substituted aryl group.
　上記カルベニウムカチオンとして具体的には、トリフェニルカルベニウムカチオン、トリス（４－メチルフェニル）カルベニウムカチオン、トリス（３，５－ジメチルフェニル）カルベニウムカチオンなどの三置換カルベニウムカチオンなどが挙げられる。 Specific examples of the carbenium cations include triphenylcarbenium cations, tris(4-methylphenyl)carbenium cations, and trisubstituted carbenium cations such as tris(3,5-dimethylphenyl)carbenium cations. .
　上記アンモニウムカチオンとして具体的には、トリメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、トリ（ｎ－プロピル）アンモニウムカチオン、トリイソプロピルアンモニウムカチオン、トリ（ｎ－ブチル）アンモニウムカチオン、トリイソブチルアンモニウムカチオンなどのトリアルキル置換アンモニウムカチオン、Ｎ，Ｎ－ジメチルアニリニウムカチオン、Ｎ，Ｎ－ジエチルアニリニウムカチオン、Ｎ，Ｎ－２，４，６－ペンタメチルアニリニウムカチオンなどのＮ，Ｎ－ジアルキルアニリニウムカチオン、ジイソプロピルアンモニウムカチオン、ジシクロヘキシルアンモニウムカチオンなどのジアルキルアンモニウムカチオンなどが挙げられる。 Specific examples of the ammonium cation include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation. cations, N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, and dialkylammonium cations such as dicyclohexylammonium cations.
　上記ホスホニウムカチオンとして具体的には、トリフェニルホスホニウムカチオン、トリス（４－メチルフェニル）ホスホニウムカチオン、トリス（３，５－ジメチルフェニル）ホスホニウムカチオンなどのトリアリールホスホニウムカチオンなどが挙げられる。 Specific examples of the phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cations, tris(4-methylphenyl)phosphonium cations, and tris(3,5-dimethylphenyl)phosphonium cations.
　Ｒe+としては、上記具体例のうち、カルベニウムカチオン、アンモニウムカチオンなどが好ましく、特にトリフェニルカルベニウムカチオン、Ｎ，Ｎ－ジメチルアニリニウムカチオン、Ｎ，Ｎ－ジエチルアニリニウムカチオンが好ましい。 Of the above specific examples, R e+ is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.
　本発明において好ましく使用されるイオン化イオン性化合物のうち、カルベニウムカチオンを含む化合物として、トリフェニルカルベニウムテトラフェニルボレート、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルカルベニウムテトラキス｛３，５－ジ－（トリフルオロメチル）フェニル｝ボレート、トリス（４－メチルフェニル）カルベニウムテトラキス（ペンタフルオロフェニル）ボレート、トリス（３，５－ジメチルフェニル）カルベニウムテトラキス（ペンタフルオロフェニル）ボレートなどを例示することができる。 Among the ionizable ionic compounds preferably used in the present invention, compounds containing carbenium cations include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis {3, 5-di-(trifluoromethyl)phenyl}borate, tris(4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, etc. can be exemplified.
　本発明において好ましく使用されるイオン化イオン性化合物のうち、トリアルキル置換アンモニウムカチオンを含む化合物として、トリエチルアンモニウムテトラフェニルボレート、トリプロピルアンモニウムテトラフェニルボレート、トリ（ｎ－ブチル）アンモニウムテトラフェニルボレート、トリメチルアンモニウムテトラキス（４－メチルフェニル）ボレート、トリメチルアンモニウムテトラキス（２－メチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリエチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリプロピルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリプロピルアンモニウムテトラキス（２，４－ジメチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（３，５－ジメチルフェニル）ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス｛４－（トリフルオロメチル）フェニル｝ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス｛３，５－ジ（トリフルオロメチル）フェニル｝ボレート、トリ（ｎ－ブチル）アンモニウムテトラキス（２－メチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラフェニルボレート、ジオクタデシルメチルアンモニウムテトラキス（４－メチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（４－メチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（２，４－ジメチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス（３，５－ジメチルフェニル）ボレート、ジオクタデシルメチルアンモニウムテトラキス｛４－（トリフルオロメチル）フェニル｝ボレート、ジオクタデシルメチルアンモニウムテトラキス｛３，５－ジ（トリフルオロメチル）フェニル｝ボレート、ジオクタデシルメチルアンモニウムなどを例示することができる。 Among the ionizable ionic compounds preferably used in the present invention, compounds containing trialkyl-substituted ammonium cations include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and trimethylammonium. tetrakis(4-methylphenyl)borate, trimethylammonium tetrakis(2-methylphenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis ( pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis{4-( trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis(2-methylphenyl)borate, dioctadecylmethyl ammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2 ,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis{4-(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium tetrakis{3,5- Examples include di(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium and the like.
　本発明において好ましく使用されるイオン化イオン性化合物のうち、Ｎ，Ｎ－ジアルキルアニリニウムカチオンを含む化合物として、Ｎ，Ｎ－ジメチルアニリニウムテトラフェニルボレート、Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジメチルアニリニウムテトラキス｛３，５－ジ（トリフルオロメチル）フェニル｝ボレート、Ｎ，Ｎ－ジエチルアニリニウムテトラフェニルボレート、Ｎ，Ｎ－ジエチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジエチルアニリニウムテトラキス｛３，５－ジ（トリフルオロメチル）フェニル｝ボレート、Ｎ，Ｎ－２，４，６－ペンタメチルアニリニウムテトラフェニルボレート、Ｎ，Ｎ－２，４，６－ペンタメチルアニリニウムテトラキス（ペタフルオロフェニル）ボレートなどを例示することができる。 Among the ionizable ionic compounds preferably used in the present invention, compounds containing N,N-dialkylanilinium cations include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl ) borate, N,N-dimethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl) Borate, N,N-diethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N,N-2,4 , 6-pentamethylanilinium tetrakis(petafluorophenyl)borate and the like.
　本発明において好ましく使用されるイオン化イオン性化合物のうち、ジアルキルアンモニウムカチオンを含む化合物として、ジ－ｎ－プロピルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジシクロヘキシルアンモニウムテトラフェニルボレートなどを例示することができる。 Among the ionizable ionic compounds preferably used in the present invention, di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate and the like can be exemplified as compounds containing dialkylammonium cations.
　その他、特開２００４－５１６７６号公報によって例示されているイオン性化合物も制限無く使用が可能である。 In addition, ionic compounds exemplified in JP-A-2004-51676 can also be used without restriction.
　上記のイオン性化合物（ｂ－３）は、１種単独で用いてもよく２種以上を混合して用いでもよい。 The above ionic compound (b-3) may be used alone or in combination of two or more.
　有機金属化合物（ｂ－１）としては、市販品のために入手が容易なトリメチルアルミニウム、トリエチルアルミニウムおよびトリイソブチルアルミニウムが好ましい。このうち、取り扱いが容易なトリイソブチルアルミニウムが特に好ましい。 As the organometallic compound (b-1), trimethylaluminum, triethylaluminum and triisobutylaluminum, which are commercially available and readily available, are preferred. Among these, triisobutylaluminum is particularly preferable because it is easy to handle.
　有機アルミニウムオキシ化合物（ｂ－２）としては、市販品のために入手が容易なメチルアルミノキサン、およびトリメチルアルミニウムとトリイソブチルアルミニウムを用いて調製したＭＭＡＯが好ましい。このうち、各種溶媒への溶解性および保存安定性が改良されたＭＭＡＯが特に好ましい。 As the organoaluminumoxy compound (b-2), methylaluminoxane, which is a commercially available product and is readily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Among these, MMAO, which has improved solubility in various solvents and improved storage stability, is particularly preferred.
　イオン性化合物（ｂ－３）としては、市販品として入手が容易であり、かつ重合活性向上への寄与が大きいことから、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートおよびＮ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレートが好ましい。 As the ionic compound (b-3), triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylaniline are readily available as commercial products and greatly contribute to the improvement of polymerization activity. Nium tetrakis(pentafluorophenyl)borate is preferred.
　化合物（ｂ）としては、重合活性が大きく向上することから、トリイソブチルアルミニウムとトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートとの組合せ、およびトリイソブチルアルミニウムとＮ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレートとの組合せが特に好ましい。 As the compound (b), a combination of triisobutylaluminum and triphenylcarbenium tetrakis(pentafluorophenyl)borate, and a combination of triisobutylaluminum and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are used, since they significantly improve the polymerization activity. A combination with fluorophenyl)borate is particularly preferred.
　＜担体（ｃ）＞
　本発明では、オレフィン重合触媒の構成成分として、必要に応じて担体（ｃ）を用いてもよい。 <Carrier (c)>
In the present invention, a carrier (c) may optionally be used as a component of the olefin polymerization catalyst.
　本発明で用いてもよい担体（ｃ）は、無機または有機の化合物であって、顆粒状ないしは微粒子状の固体である。このうち無機化合物としては、多孔質酸化物、無機塩化物、粘土、粘土鉱物またはイオン交換性層状化合物が好ましい。 The carrier (c) that may be used in the present invention is an inorganic or organic compound, and is a granular or particulate solid. Among these inorganic compounds, porous oxides, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds are preferred.
　多孔質酸化物として、具体的にはＳｉＯ2、Ａｌ2Ｏ3、ＭｇＯ、ＺｒＯ、ＴｉＯ2、Ｂ2Ｏ3、ＣａＯ、ＺｎＯ、ＢａＯ、ＴｈＯ2など、またはこれらを含む複合物または混合物、例えば天然または合成ゼオライト、ＳｉＯ2－ＭｇＯ、ＳｉＯ2－Ａｌ2Ｏ3、ＳｉＯ2－ＴｉＯ2、ＳｉＯ2－Ｖ2Ｏ5、ＳｉＯ2－Ｃｒ2Ｏ3、ＳｉＯ2－ＴｉＯ2－ＭｇＯなどを使用することができる。これらのうち、ＳｉＯ2および／またはＡｌ2Ｏ3を主成分とするものが好ましい。このような多孔質酸化物は、種類および製法によりその性状は異なるが、本発明に好ましく用いられる担体は、粒径が０．５～３００μｍ、好ましくは１．０～２００μｍであって、比表面積が５０～１０００ｍ2／ｇ、好ましくは１００～７００ｍ2／ｇの範囲にあり、細孔容積が０．３～３．０ｃｍ3／ｇの範囲にある。このような担体は、必要に応じて１００～１０００℃、好ましくは１５０～７００℃で焼成してから使用される。 Examples of porous oxides include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and the like, or composites or mixtures containing these, such as Using natural or synthetic zeolite, SiO2 - MgO, SiO2 - Al2O3 , SiO2 - TiO2 , SiO2 - V2O5 , SiO2 - Cr2O3 , SiO2 - TiO2 - MgO , etc. can do. Among these, those containing SiO 2 and/or Al 2 O 3 as main components are preferred. The properties of such porous oxides vary depending on the type and manufacturing method. is in the range of 50-1000 m 2 /g, preferably 100-700 m 2 /g, and the pore volume is in the range of 0.3-3.0 cm 3 /g. Such a carrier is used after being calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.
　無機塩化物としては、ＭｇＣｌ2、ＭｇＢｒ2、ＭｎＣｌ2、ＭｎＢｒ2等が用いられる。無機塩化物は、そのまま用いてもよいし、ボールミル、振動ミルにより粉砕した後に用いてもよい。また、アルコールなどの溶媒に無機塩化物を溶解させた後、析出剤によって微粒子状に析出させたものを用いてもよい。 As inorganic chlorides, MgCl 2 , MgBr 2 , MnCl 2 , MnBr 2 and the like are used. The inorganic chloride may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic chloride in a solvent such as alcohol, the inorganic chloride may be precipitated in the form of fine particles using a precipitating agent.
　粘土は、通常粘土鉱物を主成分として構成される。また、イオン交換性層状化合物は、イオン結合などによって、構成される面が互いに弱い結合力で平行に積み重なった結晶構造を有する化合物であり、含まれるイオンが交換可能なものである。大部分の粘土鉱物はイオン交換性層状化合物である。また、これらの粘土、粘土鉱物、イオン交換性層状化合物としては、天然産のものに限らず、人工合成物を使用することもできる。また、粘土、粘土鉱物またはイオン交換性層状化合物として、粘土、粘土鉱物、また、六方細密パッキング型、アンチモン型、ＣｄＣｌ2型、ＣｄＩ2型などの層状の結晶構造を有するイオン結晶性化合物などを例示することができる。このような粘土、粘土鉱物としては、カオリン、ベントナイト、木節粘土、ガイロメ粘土、アロフェン、ヒシンゲル石、パイロフィライト、ウンモ群、モンモリロナイト群、バーミキュライト、リョクデイ石群、パリゴルスカイト、カオリナイト、ナクライト、ディッカイト、ハロイサイトなどが挙げられ、イオン交換性層状化合物としては、α－Ｚｒ（ＨＡｓＯ4）2・Ｈ2Ｏ、α－Ｚｒ（ＨＰＯ4）2、α－Ｚｒ（ＫＰＯ4）2・３Ｈ2Ｏ、α－Ｔｉ（ＨＰＯ4）2、α－Ｔｉ（ＨＡｓＯ4）2・Ｈ2Ｏ、α－Ｓｎ（ＨＰＯ4）2・Ｈ2Ｏ、γ－Ｚｒ（ＨＰＯ4）2、γ－Ｔｉ（ＨＰＯ4）2、γ－Ｔｉ（ＮＨ4ＰＯ4）2・Ｈ2Ｏなどの多価金属の結晶性酸性塩などが挙げられる。本発明で用いられる粘土、粘土鉱物には、化学処理を施すことも好ましい。化学処理としては、表面に付着している不純物を除去する表面処理、粘土の結晶構造に影響を与える処理など、何れも使用できる。化学処理として、具体的には、酸処理、アルカリ処理、塩類処理、有機物処理などが挙げられる。 Clay is usually composed mainly of clay minerals. An ion-exchangeable layered compound is a compound having a crystal structure in which planes are stacked in parallel with a weak bonding force due to ionic bonds or the like, and the ions contained therein can be exchanged. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used. Clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type are used as clays, clay minerals, or ion-exchangeable layered compounds. can be exemplified. Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite. , halloysite, etc., and the ion-exchangeable layered compounds include α-Zr(HAsO 4 ) 2.H 2 O, α-Zr(HPO 4 ) 2 , α-Zr(KPO 4 ) 2.3H 2 O, α-Ti( HPO4 ) 2 , α-Ti( HAsO4 )2.H2O, α-Sn( HPO4 ) 2.H2O , γ-Zr( HPO4 ) 2 , γ - Ti ( HPO4 ) 2 and crystalline acid salts of polyvalent metals such as γ-Ti(NH 4 PO 4 ) 2 ·H 2 O and the like. It is also preferable to chemically treat the clay and clay mineral used in the present invention. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.
　イオン交換性層状化合物は、イオン交換性を利用し、層間の交換性イオンを別の大きな嵩高いイオンと交換することにより、層間が拡大した状態の層状化合物であってもよい。このような嵩高いイオンは、層状構造を支える支柱的な役割を担っており、通常、ピラーと呼ばれる。また、このように層状化合物の層間に別の物質（ゲスト化合物）を導入することをインターカレーションという。ゲスト化合物としては、ＴｉＣｌ4、ＺｒＣｌ4などの陽イオン性無機化合物、Ｔｉ（ＯＲ）4、Ｚｒ（ＯＲ）4、ＰＯ（ＯＲ）3、Ｂ（ＯＲ）3などの金属アルコキシド（Ｒは炭化水素基など）、［Ａｌ13Ｏ4（ＯＨ）24］7+、［Ｚｒ4（ＯＨ）14］2+、［Ｆｅ3Ｏ（ＯＣＯＣＨ3）6］+などの金属水酸化物イオンなどが挙げられる。これらの化合物は１種単独でまたは２種以上組み合わせて用いられる。また、これらの化合物をインターカレーションする際に、Ｓｉ（ＯＲ）4、Ａｌ（ＯＲ）3、Ｇｅ（ＯＲ）4などの金属アルコキシド（Ｒは炭化水素基など）などを加水分解重縮合して得た重合物、ＳｉＯ2などのコロイド状無機化合物などを共存させることもできる。また、ピラーとしては、上記金属水酸化物イオンを層間にインターカレーションした後に加熱脱水することにより生成する酸化物などが挙げられる。 The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance (guest compound) between the layers of a layered compound is called intercalation. Guest compounds include cationic inorganic compounds such as TiCl 4 and ZrCl 4 , metal alkoxides such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon groups), [ Al13O4 ( OH) 24 ] 7+ , [ Zr4 (OH) 14 ] 2+ , [ Fe3O ( OCOCH3 ) 6 ] + , metal hydroxide ions such as . These compounds are used singly or in combination of two or more. Further, when intercalating these compounds, metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4 are hydrolyzed and polycondensed. The resulting polymer, a colloidal inorganic compound such as SiO 2 , etc., can also coexist. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.
　これらのうち、好ましいものは粘土または粘土鉱物であり、特に好ましいものはモンモリロナイト、バーミキュライト、ペクトライト、テニオライトおよび合成雲母である。 Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
　担体（ｃ）としての有機化合物としては、粒径が０．５～３００μｍの範囲にある顆粒状ないしは微粒子状固体を挙げることができる。具体的には、エチレン、プロピレン、１－ブテン、４－メチル－１－ペンテンなどの炭素原子数が２～１４のα－オレフィンを主成分として生成される（共）重合体またはビニルシクロヘキサン、スチレンを主成分として生成される（共）重合体、およびそれらの変成体を例示することができる。 Examples of the organic compound as the carrier (c) include granular or particulate solids with a particle size in the range of 0.5 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.
　ランダム性の高い（Ｃ）エチレン－α－オレフィン共重合体を生成可能なオレフィン重合触媒を使用する重合方法により、高温重合が可能となる。すなわち、該オレフィン重合触媒を使用することにより、高温重合時に生成する（Ｃ）エチレン－α－オレフィン共重合体のランダム性の低下を抑制することができる。溶液重合においては、生成した（Ｃ）エチレン－α－オレフィン共重合体を含む重合溶液の粘度が高温で低下するため、低温重合時に比べて重合器内の（Ｃ）エチレン－α－オレフィン共重合体の濃度を上げることが可能となり、結果として重合器当りの生産性が向上する。本発明におけるエチレンおよびα－オレフィンの共重合は、溶液重合、懸濁重合（スラリー重合）などの液相重合法または気相重合法のいずれにおいても実施できるが、このように、本発明の効果を最大限享受し得るという観点からは溶液重合が特に好ましい。 High-temperature polymerization is possible with a polymerization method that uses an olefin polymerization catalyst capable of producing (C) ethylene-α-olefin copolymer with high randomness. That is, by using the olefin polymerization catalyst, it is possible to suppress the decrease in the randomness of the (C) ethylene-α-olefin copolymer produced during high-temperature polymerization. In solution polymerization, the viscosity of the polymerization solution containing the (C) ethylene-α-olefin copolymer produced decreases at high temperatures, so the (C) ethylene-α-olefin copolymer in the polymerization vessel is lower than during low-temperature polymerization. It is possible to increase the coalescence concentration, resulting in an improvement in productivity per polymerization vessel. Copolymerization of ethylene and α-olefin in the present invention can be carried out by either liquid phase polymerization method such as solution polymerization or suspension polymerization (slurry polymerization) or gas phase polymerization method. Solution polymerization is particularly preferred from the viewpoint of being able to enjoy the maximum.
　オレフィン重合触媒の各成分の使用法、添加順序は任意に選ばれる。また、触媒中の各成分の少なくとも２つ以上は予め接触されていてもよい。 The usage and order of addition of each component of the olefin polymerization catalyst are arbitrarily selected. At least two or more of each component in the catalyst may be contacted in advance.
　架橋メタロセン化合物（ａ）（以下「成分（ａ）」ともいう。）は、反応容積１リットル当り、通常１×１０-9～１×１０-1モル、好ましくは１×１０-8～１×１０-2モルになるような量で用いられる。 The amount of the bridged metallocene compound (a) (hereinafter also referred to as "component (a)") is generally 1×10 -9 to 1×10 -1 mol, preferably 1×10 -8 to 1×10 -1 mol, per liter of reaction volume. It is used in an amount to give 10 -2 mol.
　有機金属化合物（ｂ－１）（以下「成分（ｂ－１）」ともいう。）は、成分（ｂ－１）と、成分（ａ）中の遷移金属原子（Ｍ）とのモル比［（ｂ－１）／Ｍ］が、通常０．０１～５０，０００、好ましくは０．０５～１０，０００となるような量で用いられる。 The organometallic compound (b-1) (hereinafter also referred to as “component (b-1)”) has a molar ratio [( b-1)/M] is usually 0.01 to 50,000, preferably 0.05 to 10,000.
　有機アルミニウムオキシ化合物（ｂ－２）（以下「成分（ｂ－２）」ともいう。）は、成分（ｂ－２）中のアルミニウム原子と、成分（ａ）中の遷移金属原子（Ｍ）とのモル比［（ｂ－２）／Ｍ］が、通常１０～５，０００、好ましくは２０～２，０００となるような量で用いられる。 The organoaluminumoxy compound (b-2) (hereinafter also referred to as "component (b-2)") is composed of the aluminum atom in component (b-2) and the transition metal atom (M) in component (a). is used in such an amount that the molar ratio [(b-2)/M] of is usually 10 to 5,000, preferably 20 to 2,000.
　イオン性化合物（ｂ－３）（以下「成分（ｂ－３）」ともいう。）は、成分（ｂ－３）と、成分（ａ）中の遷移金属原子（Ｍ）とのモル比［（ｂ－３）／Ｍ］が、通常１～１０，０００、好ましくは１～５，０００となるような量で用いられる。 The ionic compound (b-3) (hereinafter also referred to as "component (b-3)") has a molar ratio [( b-3)/M] is usually 1 to 10,000, preferably 1 to 5,000.
　重合温度は、通常－５０℃～３００℃であり、好ましくは３０～２５０℃、より好ましくは１００℃～２５０℃、さらに好ましくは１３０℃～２００℃である。前記範囲の重合温度領域では温度が高くなるに従い、重合時の溶液粘度が低下し、重合熱の除熱も容易となる。重合圧力は、通常、常圧～１０ＭＰａゲージ圧（ＭＰａ－Ｇ）、好ましくは常圧～８ＭＰａ－Ｇである。 The polymerization temperature is usually -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, still more preferably 130°C to 200°C. In the polymerization temperature range within the above range, the higher the temperature, the lower the viscosity of the solution during polymerization, making it easier to remove the heat of polymerization. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.
　重合反応は、回分式、半連続式、連続式のいずれの方法においても行うことができる。さらに、重合を反応条件の異なる二つ以上の重合器で連続的に行うことも可能である。 The polymerization reaction can be carried out in any of batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.
　得られる共重合体の分子量は、重合系中の水素濃度や重合温度を変化させることによって調節することができる。さらに、使用する成分（ｂ）の量により調節することもできる。水素を添加する場合、その量は生成する共重合体１ｋｇあたり０．００１～５，０００ＮＬ程度が適当である。 The molecular weight of the obtained copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can also be adjusted by the amount of component (b) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of copolymer produced.
　液相重合法において用いられる重合溶媒は、通常、不活性炭化水素溶媒であり、好ましくは常圧下における沸点が５０℃～２００℃の飽和炭化水素である。重合溶媒としては、具体的には、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油などの脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロペンタンなどの脂環族炭化水素が挙げられ、特に好ましくは、ヘキサン、ヘプタン、オクタン、デカン、シクロヘキサンが挙げられる。重合対象であるα－オレフィン自身を重合溶媒として用いることもできる。尚、ベンゼン、トルエン、キシレンなどの芳香族炭化水素類やエチレンクロリド、クロルベンゼン、ジクロロメタンなどのハロゲン化炭化水素も重合溶媒として使用することができるが、環境への負荷軽減の視点および人体健康への影響の最少化の視点からは、これらの使用は好ましくない。 The polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure. Specific examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. and particularly preferably hexane, heptane, octane, decane, and cyclohexane. The α-olefin to be polymerized itself can also be used as a polymerization solvent. Aromatic hydrocarbons such as benzene, toluene, and xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents. From the viewpoint of minimizing the impact of
　オレフィン重合体の１００℃における動粘度は重合体の分子量に依存する。すなわち高分子量であれば高粘度となり、低分子量であれば低粘度となるため、上述の分子量調整により１００℃における動粘度を調整する。また、減圧蒸留のような従来公知の方法により得られた重合体の低分子量成分を除去することで、得られる重合体の分子量分布（Ｍｗ／Ｍｎ）を調整することができる。さらに得られた重合体について、従来公知の方法により水素添加（以下水添ともいう。）を行ってもよい。水添により得られた重合体の２重結合が低減されれば、酸化安定性および耐熱性が向上する。 The kinematic viscosity of olefin polymers at 100°C depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity will be high, and if the molecular weight is low, the viscosity will be low. In addition, the molecular weight distribution (Mw/Mn) of the resulting polymer can be adjusted by removing low molecular weight components from the polymer obtained by a conventionally known method such as vacuum distillation. Furthermore, the obtained polymer may be hydrogenated (hereinafter also referred to as hydrogenation) by a conventionally known method. If the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.
　得られた（Ｃ）エチレン－α－オレフィン共重合体は、１種単独で用いてもよく、また、異なる分子量のものや異なるモノマー組成のものを２種類以上組み合わせてもよい。 The obtained (C) ethylene-α-olefin copolymer may be used alone, or two or more of them having different molecular weights or different monomer compositions may be used in combination.
　また、（Ｃ）エチレン－α－オレフィン共重合体は、官能基をグラフト変性させてもよく、また、これらをさらに２次変性してもよい。例えば、特開昭６１－１２６１２０号公報や特許第２５９３２６４号公報などに記載される方法など、２次変性としては特表２００８－５０８４０２号公報などに記載される方法などが挙げられる。 In addition, (C) the ethylene-α-olefin copolymer may be graft modified with functional groups, or these may be further modified secondary. For example, the methods described in JP-A-61-126120, JP-A-2593264, etc., and secondary modification include the methods described in JP-A-2008-508402.
　＜（Ａ）鉱物油＞
　（Ａ）鉱物油は以下（Ａ１）～（Ａ３）の特徴を有する。 <(A) Mineral oil>
(A) Mineral oil has the following characteristics (A1) to (A3).
　（Ａ１）１００℃における動粘度が２～６ｍｍ2／ｓであること
　この１００℃動粘度の値はＪＩＳ Ｋ２２８３に記載の方法に従い測定した場合のものである。（Ａ）鉱物油の１００℃における動粘度は、２～８ｍｍ2／ｓ、好ましくは２．３～５．５ｍｍ2／ｓ、より好ましくは２．８～５ｍｍ2／ｓである。１００℃における動粘度がこの範囲にあると、本発明の潤滑油組成物は、揮発性、温度粘度特性のバランスの観点において優れる。 (A1) Kinematic viscosity at 100° C. is 2 to 6 mm 2 /s This value of kinematic viscosity at 100° C. is measured according to the method described in JIS K2283. (A) The kinematic viscosity at 100° C. of mineral oil is 2 to 8 mm 2 /s, preferably 2.3 to 5.5 mm 2 /s, more preferably 2.8 to 5 mm 2 /s. When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the present invention is excellent in terms of the balance between volatility and temperature-viscosity characteristics.
　（Ａ２）粘度指数が１０５以上であること
この粘度指数の値はＪＩＳ Ｋ２２８３に記載の方法に従い測定した場合のものである。（Ａ）鉱物油の粘度指数は、１０５以上、好ましくは１１０以上、さらに好ましくは１１５以上である。粘度指数がこの範囲にあると、本発明の潤滑油組成物は優れた温度粘度特性を有する。 (A2) Viscosity index is 105 or more This value of viscosity index is measured according to the method described in JIS K2283. (A) The mineral oil has a viscosity index of 105 or higher, preferably 110 or higher, and more preferably 115 or higher. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature-viscosity characteristics.
　（Ａ３）流動点が－５℃以下であること
　この流動点の値はＡＳＴＭ　Ｄ９７に記載の方法に従い測定した場合のものである。（Ａ）鉱物油の流動点は、－５℃以下、より好ましくは－１０℃以下、さらに好ましくは－１２℃以下である。流動点がこの範囲にあると、本発明の潤滑油組成物は優れた低温粘度特性を有する。 (A3) Pour point is −5° C. or less This value of pour point is measured according to the method described in ASTM D97. (A) The pour point of the mineral oil is -5°C or lower, more preferably -10°C or lower, and still more preferably -12°C or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
　＜（Ｂ）合成油＞
　（Ｂ）合成油は以下（Ｂ１）～（Ｂ３）の特徴を有する。 <(B) Synthetic oil>
(B) The synthetic oil has the following characteristics (B1) to (B3).
　（Ｂ１）１００℃における動粘度が１～９ｍｍ2／ｓであること
　この１００℃動粘度の値はＪＩＳ Ｋ２２８３に記載の方法に従い測定した場合のものである。（Ｂ）合成油の１００℃における動粘度は、１～９ｍｍ2／ｓ、好ましくは１．５～７ｍｍ2／ｓ、より好ましくは１．８～５ｍｍ2／ｓである。１００℃における動粘度がこの範囲にあると、本発明の潤滑油組成物は、揮発性、温度粘度特性のバランスの観点において優れる。 (B1) Kinematic viscosity at 100° C. is 1 to 9 mm 2 /s This value of kinematic viscosity at 100° C. is measured according to the method described in JIS K2283. (B) The kinematic viscosity at 100° C. of the synthetic oil is 1 to 9 mm 2 /s, preferably 1.5 to 7 mm 2 /s, more preferably 1.8 to 5 mm 2 /s. When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the present invention is excellent in terms of the balance between volatility and temperature-viscosity characteristics.
　（Ｂ２）粘度指数が１１０以上であること
　この粘度指数の値はＪＩＳ Ｋ２２８３に記載の方法に従い測定した場合のものである。（Ｂ）合成油の粘度指数は、１１０以上、好ましくは１１５以上、より好ましくは１２０以上である。粘度指数がこの範囲にあると、本発明の潤滑油組成物は優れた温度粘度特性を有する。 (B2) Viscosity index is 110 or more This value of viscosity index is measured according to the method described in JIS K2283. (B) The synthetic oil has a viscosity index of 110 or higher, preferably 115 or higher, more preferably 120 or higher. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature-viscosity characteristics.
　（Ｂ３）流動点が－３０℃以下であること
　この流動点の値はＡＳＴＭ　Ｄ９７に記載の方法に従い測定した場合のものである。（Ｂ）合成油の流動点は、－３０℃以下、好ましくは－４０℃以下、より好ましくは－５０℃以下、さらに好ましくは－６０℃以下である。流動点がこの範囲にあると、本発明の潤滑油組成物は優れた低温粘度特性を有する。 (B3) Pour point is −30° C. or lower This value of pour point is measured according to the method described in ASTM D97. (B) The pour point of the synthetic oil is -30°C or lower, preferably -40°C or lower, more preferably -50°C or lower, and still more preferably -60°C or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity properties.
　本発明に使用される潤滑油基油は、その製造方法や精製方法等により粘度特性や耐熱性、酸化安定性等の性能・品質が異なるが、一般に鉱物油と合成油とに大別される。また、ＡＰＩ（Ａｍｅｒｉｃａｎ　Ｐｅｔｒｏｌｅｕｍ　Ｉｎｓｔｉｔｕｔｅ）では、潤滑油基油をグループＩ、ＩＩ、ＩＩＩ、ＩＶ、Ｖの５種類に分類している。これらＡＰＩカテゴリーはＡＰＩ Ｐｕｂｌｉｃａｔｉｏｎ １５０９、１５ｔｈ Ｅｄｉｔｉｏｎ、Ａｐｐｅｎｄｉｘ Ｅ、Ａｐｒｉｌ ２００２において定義されており、表１に示すとおりである。（Ａ）鉱物油はＡＰＩカテゴリーにおけるグループＩ～ＩＩＩのいずれでも良く、（Ｂ）合成油はＡＰＩカテゴリーにおけるグループＩＶおよびＶのいずれでも良い。以下に詳細を記す。 The lubricating base oil used in the present invention varies in performance and quality such as viscosity characteristics, heat resistance, and oxidation stability depending on the manufacturing method and refining method, but is generally divided into mineral oil and synthetic oil. . In addition, API (American Petroleum Institute) classifies lubricating base oils into five types of groups I, II, III, IV and V. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002, and are shown in Table 1. (A) Mineral oils may be any of Groups I-III in the API category and (B) Synthetic oils may be any of Groups IV and V in the API category. Details are given below.
Figure JPOXMLDOC01-appb-T000012
 ＊１：ＡＳＴＭ　Ｄ４４５（ＪＩＳ　Ｋ２２８３）に準じて測定
＊２：ＡＳＴＭ　Ｄ３３３８に準じて測定
＊３：ＡＳＴＭ　Ｄ４２９４（ＪＩＳ　Ｋ２５４１）に準じて測定
＊２：飽和炭化水素が９０ｖｏｌ％未満でかつ硫黄分が０．０３重量％を超える鉱物油もグループＩに含まれる。
Figure JPOXMLDOC01-appb-T000012
 *1: Measured according to ASTM D445 (JIS K2283) *2: Measured according to ASTM D3338 *3: Measured according to ASTM D4294 (JIS K2541) *2: Saturated hydrocarbon is less than 90 vol% and sulfur content is Group I also includes mineral oils in excess of 0.03% by weight.
　＜（Ａ）鉱物油＞
　（Ａ）鉱物油は、上述のＡＰＩカテゴリーにおけるグループＩ～ＩＩＩに帰属される。 <(A) Mineral oil>
(A) Mineral oils are assigned to Groups I-III in the API category described above.
　（Ａ）鉱物油の品質は上述の通りであり、精製の方法により、上述したそれぞれの品質の鉱物油が得られる。鉱物油としては、具体的には、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油等の潤滑油基油が例示できる。 (A) The quality of the mineral oil is as described above, and the mineral oil of each quality described above can be obtained by the refining method. As the mineral oil, specifically, the lubricating oil fraction obtained by vacuum distillation of the atmospheric residue obtained by atmospheric distillation of crude oil is subjected to solvent deasphalting, solvent extraction, hydrocracking, solvent deasphalting. Lubricating base oils such as those refined by one or more treatments such as waxes, hydrorefining, or wax isomerized mineral oils can be exemplified.
　また、フィッシャー・トロプシュ法によって得られたガス・トゥー・リキッド（ＧＴＬ）基油もグループＩＩＩ鉱物油として好適に用いることのできる基油である。このようなＧＴＬ基油は、グループＩＩＩ＋潤滑油基油として扱われることもあり、例えば、特許文献であるＥＰ０７７６９５９、ＥＰ０６６８３４２、ＷＯ９７／２１７８８、ＷＯ００／１５７３６、ＷＯ００／１４１８８、ＷＯ００／１４１８７、ＷＯ００／１４１８３、ＷＯ００／１４１７９、ＷＯ００／０８１１５、ＷＯ９９／４１３３２、ＥＰ１０２９０２９、ＷＯ０１／１８１５６およびＷＯ０１／５７１６６に記載されている。 A gas-to-liquid (GTL) base oil obtained by the Fischer-Tropsch process is also a base oil that can be suitably used as a Group III mineral oil. Such GTL base oils may also be treated as Group III+ lubricant base oils, e.g. , WO00/14179, WO00/08115, WO99/41332, EP1029029, WO01/18156 and WO01/57166.
　＜（Ｂ）合成油＞
　（Ｂ）合成油は、上述のＡＰＩカテゴリーにおけるグループＩＶ、またはグループＶに帰属される。 <(B) Synthetic oil>
(B) Synthetic oils are assigned to Group IV or Group V in the API categories described above.
　グループＩＶに帰属されるポリ－α－オレフィンは米国特許第３，３８２，２９１号公報、米国特許第３，７６３，２４４号公報、米国特許第５，１７１，９０８号公報、米国特許第３，７８０，１２８号公報、米国特許第４，０３２，５９１号公報、特開平１－１６３１３６号公報、米国特許第４，９６７，０３２号公報、米国特許４，９２６，００４号公報に記載のように三フッ化ホウ素、クロム酸触媒等の酸触媒によるオリゴメリゼーションにより得ることができる。また、特開昭６３－０３７１０２号公報、特開２００５－２００４４７号公報、特開２００５－２００４４８号公報、特表２００９－５０３１４７号公報、特表２００９－５０１８３６号公報に記載のようなメタロセン化合物を含むジルコニウム、チタン、ハフニウム等の遷移金属錯体を用いた触媒系を用いる方法等によっても得ることができる。前記潤滑油基油としてポリ－α－オレフィンを用いると、極めて温度粘度特性、低温粘度特性、さらには耐熱性に優れた潤滑油組成物が得られる。 Poly-α-olefins belonging to Group IV are disclosed in US Pat. No. 3,382,291, US Pat. No. 3,763,244, US Pat. 780,128, US Pat. No. 4,032,591, JP-A-1-163136, US Pat. No. 4,967,032, US Pat. No. 4,926,004 It can be obtained by oligomerization with an acid catalyst such as boron trifluoride or a chromic acid catalyst. Further, a metallocene compound as described in JP-A-63-037102, JP-A-2005-200447, JP-A-2005-200448, JP-A-2009-503147, JP-A-2009-501836. It can also be obtained by a method using a catalyst system using a transition metal complex of zirconium, titanium, hafnium, or the like. When poly-α-olefin is used as the lubricating base oil, it is possible to obtain a lubricating oil composition which is extremely excellent in temperature viscosity characteristics, low temperature viscosity characteristics, and heat resistance.
　ポリ－α－オレフィンは、工業的にも入手可能であり、１００℃動粘度２ｍｍ2／ｓ～３００ｍｍ2／ｓのものが市販されている。その中でも、２～６ｍｍ2／ｓのポリ－α－オレフィンを使用すると温度粘度特性に優れた潤滑油組成物が得られる点で好ましい。例えば、ＮＥＳＴＥ社製ＮＥＸＢＡＳＥ２０００シリーズ、ＥｘｘｏｎＭｏｂｉｌ Ｃｈｅｍｉｃａｌ社製Ｓｐｅｃｔｒａｓｙｎシリーズ、Ｉｎｅｏｓ　Ｏｌｉｇｍｅｒｓ社製Ｄｕｒａｓｙｎシリーズ、Ｃｈｅｖｒｏｎ Ｐｈｉｌｌｉｐｓ Ｃｈｅｍｉｃａｌ社製Ｓｙｎｆｌｕｉｄシリーズなどが挙げられる。 Poly-α-olefins are also commercially available, and those with kinematic viscosities at 100° C. of 2 mm 2 /s to 300 mm 2 /s are commercially available. Among them, it is preferable to use a poly-α-olefin of 2 to 6 mm 2 /s in that a lubricating oil composition having excellent temperature-viscosity characteristics can be obtained. Examples include the NEXBASE2000 series manufactured by NESTE, the Spectrasyn series manufactured by ExxonMobil Chemical, the Durasyn series manufactured by Ineos Oligmers, and the Synfluid series manufactured by Chevron Phillips Chemical.
　グループＶに帰属される合成油としては、例えばアルキルベンゼン類、アルキルナフタレン類、イソブテンオリゴマーまたはその水素化物、パラフィン類、ポリオキシアルキレングリコール、ジアルキルジフェニルエーテル、ポリフェニルエーテル、エステル等が挙げられる。 Synthetic oils belonging to Group V include, for example, alkylbenzenes, alkylnaphthalenes, isobutene oligomers or hydrides thereof, paraffins, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, and esters.
　アルキルベンゼン類、アルキルナフタレン類の大部分は、通常アルキル鎖長が炭素原子数６～１４のジアルキルベンゼンまたはジアルキルナフタレンであり、このようなアルキルベンゼン類またはアルキルナフタレン類は、ベンゼンまたはナフタレンとオレフィンとのフリーデルクラフトアルキル化反応によって製造される。アルキルベンゼン類またはアルキルナフタレン類の製造において使用されるアルキル化オレフィンは、線状もしくは枝分かれ状のオレフィンまたはこれらの組み合わせでもよい。これらの製造方法は、例えば、米国特許第３，９０９，４３２号に記載されている。 Most of alkylbenzenes and alkylnaphthalenes are usually dialkylbenzenes or dialkylnaphthalenes having an alkyl chain length of 6 to 14 carbon atoms, and such alkylbenzenes or alkylnaphthalenes are free from benzene or naphthalene and olefins. It is produced by the Delcraft alkylation reaction. Alkylated olefins used in the production of alkylbenzenes or alkylnaphthalenes can be linear or branched olefins or combinations thereof. These manufacturing methods are described, for example, in US Pat. No. 3,909,432.
　また、エステルは（Ｃ）エチレン－α－オレフィン共重合体との相溶性の観点から脂肪酸エステルが好ましい。脂肪酸エステルとしては、特に限定されないが、以下のような炭素、酸素、水素のみからなる脂肪酸エステルが挙げられ、例えば、一塩基酸とアルコールから製造されるモノエステル；二塩基酸とアルコールとから、またはジオールと一塩基酸または酸混合物とから製造されるジエステル；ジオール、トリオール（たとえばトリメチロールプロパン）、テトラオール（たとえばペンタエリスリトール）、ヘキサオール（たとえばジペンタエリスリトール）などと一塩基酸または酸混合物とを反応させて製造したポリオールエステルなどが挙げられる。これらのエステルの例としては、ジトリデシルグルタレート、ジ－２－エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ－２－エチルヘキシルセバケート、トリデシルペラルゴネート、ジ－２－エチルヘキシルアジペート、ジ－２－エチルヘキシルアゼレート、トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、トリメチロールプロパントリヘプタノエート、ペンタエリスリトール－２－エチルヘキサノエート、ペンタエリスリトールペラルゴネート、ペンタエリスリトールテトラヘプタノエートなどが挙げられる。 Also, the ester is preferably a fatty acid ester from the viewpoint of compatibility with (C) the ethylene-α-olefin copolymer. Fatty acid esters are not particularly limited, but include the following fatty acid esters consisting only of carbon, oxygen, and hydrogen. For example, monoesters produced from monobasic acid and alcohol; or diesters prepared from diols and monobasic acids or acid mixtures; diols, triols (e.g. trimethylolpropane), tetraols (e.g. pentaerythritol), hexaols (e.g. dipentaerythritol), etc. and monobasic acids or acid mixtures. and a polyol ester produced by reacting with. Examples of these esters include ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, tridecyl pelargonate, di-2-ethylhexyl adipate, di-2 -ethylhexyl azelate, trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane triheptanoate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, pentaerythritol tetraheptanoate, etc. .
　（Ｃ）エチレン－α－オレフィン共重合体との相溶性の観点から、エステルを構成するアルコール部位としては、水酸基が２官能以上のアルコールが好ましく、脂肪酸部位としては、炭素数が８以上の脂肪酸が好ましい。ただし、脂肪酸については製造コストの点において、工業的に入手が容易である炭素数が２０以下の脂肪酸が優位である。エステルを構成する脂肪酸は１種でもよく、２種以上の酸混合物を用いて製造される脂肪酸エステルを用いても、本発明の効果は十分に発揮される。脂肪酸エステルとしては、より具体的には、トリメチロールプロパンラウリン酸ステアリン酸混合トリエステルやジイソデシルアジペートなどが挙げられ、これらは（Ｃ）エチレン－α－オレフィン共重合体のような飽和炭化水素成分と、後述する極性基を有する酸化防止剤、腐食防止剤、耐摩耗剤、摩擦調整剤、流動点降下剤、防錆剤および消泡剤等の安定剤との相溶性の点から好ましい。 (C) From the viewpoint of compatibility with the ethylene-α-olefin copolymer, the alcohol moiety constituting the ester is preferably an alcohol having a hydroxyl group of two or more functional groups, and the fatty acid moiety is a fatty acid having 8 or more carbon atoms. is preferred. However, fatty acids with 20 or less carbon atoms, which are industrially readily available, are superior in terms of production cost. The fatty acid constituting the ester may be of one kind, or the effect of the present invention can be sufficiently exhibited even if a fatty acid ester produced by using a mixture of two or more kinds of acids is used. More specifically, fatty acid esters include trimethylolpropane lauric stearic acid mixed triesters and diisodecyl adipate, which are combined with saturated hydrocarbon components such as (C) ethylene-α-olefin copolymers. , from the viewpoint of compatibility with stabilizers such as antioxidants, corrosion inhibitors, antiwear agents, friction modifiers, pour point depressants, rust inhibitors and antifoaming agents having polar groups, which will be described later.
　本発明の潤滑油組成物は、潤滑油基油として（Ｂ）合成油、特にポリ－α－オレフィンを用いる場合、潤滑油組成物全体を１００質量％としたときに、脂肪酸エステルを１～２０質量％の量で含むことが好ましい。１質量％以上の脂肪酸エステルを含有することにより、電動車両における樹脂やエラストマーといった潤滑油封止材に対し、良好な適合性が得られる。具体的には、潤滑油封止材の膨潤を抑制できる。酸化安定性または耐熱性の観点から、エステルの量は２０質量％以下であることが好ましい。潤滑油組成物に鉱物油が含まれる場合、鉱物油そのものが潤滑油封止剤の膨潤抑制効果を有するため、脂肪酸エステルは必ずしも要さない。 The lubricating oil composition of the present invention contains 1 to 20 fatty acid esters when the total lubricating oil composition is 100% by mass when (B) synthetic oil, particularly poly-α-olefin, is used as the lubricating base oil. It is preferably included in the amount of % by mass. By containing 1% by mass or more of fatty acid ester, good compatibility with lubricating oil sealing materials such as resins and elastomers in electric vehicles can be obtained. Specifically, swelling of the lubricating oil sealing material can be suppressed. From the viewpoint of oxidation stability or heat resistance, the amount of ester is preferably 20% by mass or less. When the lubricating oil composition contains mineral oil, the mineral oil itself has the effect of suppressing the swelling of the lubricating oil sealant, so the fatty acid ester is not necessarily required.
　（Ｂ）合成油は、（Ａ）鉱物油に比べて耐熱性や温度粘度特性に優れている点で好ましい。本発明の潤滑油組成物においては、潤滑油基油として、（Ａ）鉱物油または（Ｂ）合成油を１種単独で用いてもよく、また、（Ａ）鉱物油、（Ｂ）合成油の中から選ばれる２種以上の潤滑油の任意混合物等を使用してもよい。 (B) Synthetic oil is preferable in that it is superior to (A) mineral oil in terms of heat resistance and temperature-viscosity characteristics. In the lubricating oil composition of the present invention, (A) mineral oil or (B) synthetic oil may be used alone as the lubricating base oil, and (A) mineral oil and (B) synthetic oil Any mixture of two or more lubricating oils selected from may be used.
　本発明に係る電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は、前記（Ａ）鉱物油、および／または（Ｂ）合成油、ならびに前記（Ｃ）エチレン－α－オレフィン共重合体を含有し、以下の（Ｄ１）の特徴を有する。 The lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention includes (A) mineral oil and/or (B) synthetic oil and (C) ethylene-α - It contains an olefin copolymer and has the following characteristics of (D1).
　（Ｄ１）１００℃における動粘度が４～１０ｍｍ2／ｓであること
　この１００℃における動粘度（ＪＩＳ Ｋ２２８３に記載の方法に従い測定される動粘度）は、４～１０ｍｍ2／ｓ、好ましくは４～７．５ｍｍ2／ｓ、より好ましく４～６．５ｍｍ2／ｓ、さらに好ましくは４．２～６ｍｍ2／ｓである。電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物の１００℃における動粘度が１０ｍｍ2／ｓを過度に超えると潤滑油のギア、もしくは金属チェーン等への撹拌抵抗が増加し、省燃費性能が劣り、４ｍｍ2／ｓよりも過度に小さいとギア、もしくは金属チェーン間での金属接触が生じる可能性がある。 (D1) Kinematic viscosity at 100°C is 4 to 10 mm 2 /s The kinematic viscosity at 100°C (kinematic viscosity measured according to the method described in JIS K2283) is 4 to 10 mm 2 /s, preferably 4 ~7.5 mm 2 /s, more preferably 4 to 6.5 mm 2 /s, still more preferably 4.2 to 6 mm 2 /s. If the kinematic viscosity at 100° C. of the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle excessively exceeds 10 mm 2 /s, the stirring resistance of the lubricating oil to the gears, metal chains, etc. If it is excessively smaller than 4 mm 2 /s, metal contact may occur between gears or metal chains.
　本発明に係る電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は、さらに（Ｄ２）、（Ｄ３）の特徴を有することが好ましい。 The lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention preferably further has characteristics (D2) and (D3).
　（Ｄ２）粘度指数が１１０以上であること
　この粘度指数（ＪＩＳ Ｋ２２８３に記載の方法に従い測定される粘度指数）は、好ましくは１１０以上、より好ましくは１２０以上、さらに好ましくは１２５以上、特に好ましくは１３０以上である。粘度指数がこの範囲であると、潤滑油組成物は優れた温度粘度特性を有し、幅広い温度で前記省エネルギー性と潤滑性を両立させることが可能となる。 (D2) Viscosity index is 110 or more This viscosity index (viscosity index measured according to the method described in JIS K2283) is preferably 110 or more, more preferably 120 or more, still more preferably 125 or more, and particularly preferably 130 or more. When the viscosity index is within this range, the lubricating oil composition has excellent temperature-viscosity characteristics, and it becomes possible to achieve both the energy saving property and lubricity over a wide range of temperatures.
　（Ｄ３）流動点が－４０℃以下であること
　本発明に係る電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物の流動点（ＡＳＴＭ　Ｄ９７に記載の方法に従って測定される流動点）は好ましくは－４０℃以下、より好ましくは－４５℃以下、さらに好ましくは－５０℃以下である。流動点が低いことは、潤滑油組成物が低温特性に優れることを示す。 (D3) The pour point is −40° C. or less The pour point of the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle according to the present invention (measured according to the method described in ASTM D97) The pour point) is preferably −40° C. or lower, more preferably −45° C. or lower, and still more preferably −50° C. or lower. A low pour point indicates that the lubricating oil composition has excellent low temperature properties.
　本発明の電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は、前記（Ａ）鉱物油、および／または（Ｂ）合成油からなる潤滑油基油を９０～９９質量％、前記（Ｃ）エチレン－α－オレフィン共重合体を１０～１質量％の割合で含有することが好ましい。ただし、前記潤滑油基油と前記（Ｃ）エチレン－α－オレフィン共重合体との合計を１００質量％とする。本発明の電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は、好ましくは、前記潤滑油基油を９２～９９質量％、前記（Ｃ）エチレン－α－オレフィン共重合体を８～１質量％の割合で、より好ましくは、前記潤滑油基油を９５～９９質量％、前記（Ｃ）エチレン－α－オレフィン共重合体を５～１質量％の割合で、さらに好ましくは、前記潤滑油基油を９６～９９質量％、前記（Ｃ）エチレン－α－オレフィン共重合体を４～１質量％の割合で含有する。 The lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention contains 90 to 99 It is preferable to contain the (C) ethylene-α-olefin copolymer in a proportion of 10 to 1% by mass. However, the total amount of the lubricating base oil and the ethylene-α-olefin copolymer (C) is 100% by mass. The lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention preferably contains 92 to 99% by mass of the lubricating base oil and the (C) ethylene-α-olefin co- 8 to 1% by mass of the polymer, more preferably 95 to 99% by mass of the lubricating base oil, and 5 to 1% by mass of the (C) ethylene-α-olefin copolymer, More preferably, it contains 96 to 99% by mass of the lubricating base oil and 4 to 1% by mass of the ethylene-α-olefin copolymer (C).
　好ましい一態様としては、潤滑油基油のうち、３０～１００質量％が（Ａ）鉱物油である態様が挙げられる。潤滑油基油に占める（Ａ）鉱物油の割合が高いと後述する添加剤の溶解性に優れるほか、入手容易で経済性に優れている。５０～１００質量％が鉱物油であるとより好ましく、８０～１００質量％が鉱物油であるとさらに好ましい。鉱物油の中では、ＡＰＩカテゴリーにおけるグループＩＩＩが、温度粘度特性に優れ、高温での油膜保持と低温での低トルクとを両立できるため、好ましい。 As a preferred embodiment, 30 to 100% by mass of the lubricating base oil is (A) mineral oil. When the proportion of (A) mineral oil in the base oil of the lubricating oil is high, the solubility of the additives described later is excellent, and the oil is easily available and economical. More preferably 50 to 100% by mass mineral oil, and even more preferably 80 to 100% by mass mineral oil. Among mineral oils, group III in the API category is preferable because it has excellent temperature-viscosity characteristics and can achieve both oil film retention at high temperatures and low torque at low temperatures.
　別の好ましい一態様としては、潤滑油基油のうち、３０～１００質量％が、（Ｂ）合成油であって、かつ（Ｂ）合成油がポリ－α－オレフィンおよび／またはエステル油である態様が挙げられる。５０～１００質量％が合成油であるとより好ましく、８０～１００質量％が合成油であるとさらに好ましい。潤滑油基油に占める（Ｂ）合成油の割合が高いと、耐熱性、温度粘度特性、低温特性が優れており、好ましい。 In another preferred embodiment, 30 to 100% by mass of the lubricating base oil is (B) synthetic oil, and (B) synthetic oil is poly-α-olefin and / or ester oil aspects. It is more preferably 50 to 100% by mass of synthetic oil, and even more preferably 80 to 100% by mass of synthetic oil. A high proportion of the synthetic oil (B) in the base oil of the lubricating oil is preferable because the heat resistance, temperature-viscosity characteristics, and low-temperature characteristics are excellent.
　また、本発明の電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は、極圧剤、清浄分散剤、粘度指数向上剤、酸化防止剤、腐食防止剤、耐摩耗剤、摩擦調整剤、流動点降下剤、防錆剤および消泡剤等の添加剤を含んでいてもよい。 In addition, the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention contains extreme pressure agents, detergent-dispersants, viscosity index improvers, antioxidants, corrosion inhibitors, anti-wear agents. additives such as agents, friction modifiers, pour point depressants, rust inhibitors and defoamers.
　本発明の潤滑油組成物に用いられる添加剤としては下記のものを例示することができ、これらを１種単独でまたは２種以上組み合わせて用いることができる。 Examples of additives used in the lubricating oil composition of the present invention include the following, and these can be used singly or in combination of two or more.
　極圧剤は、金属同士が高負荷状態に晒された場合に、焼付け防止の効果を有するものの総称であり、特に限定されないが、スルフィド類、スルホキシド類、スルホン類、チオホスフィネート類、チオカーボネート類、硫化油脂、硫化オレフィンなどのイオウ系極圧剤；リン酸エステル、亜リン酸エステル、リン酸エステルアミン塩、亜リン酸エステルアミン類などのリン酸類；塩素化炭化水素などのハロゲン系化合物などを例示することができる。また、これらの化合物を２種類以上併用してもよい。 Extreme pressure agent is a general term for substances that have an effect of preventing seizure when metals are exposed to a high load, and is not particularly limited, but includes sulfides, sulfoxides, sulfones, thiophosphinates, and thiocarbonates. Sulfur-based extreme pressure agents such as sulfurized oils and fats and sulfurized olefins; etc. can be exemplified. Also, two or more of these compounds may be used in combination.
　なお、極圧潤滑条件に至るまでに、炭化水素、または潤滑油組成物を構成する他の有機成分が、加熱、せん断により極圧潤滑条件以前に炭化してしまい、金属表面に炭化物被膜を形成する可能性がある。このため、極圧剤単独の使用では、炭化物被膜により極圧剤と金属表面の接触が阻害され、極圧剤の十分な効果が期待できないおそれがある。 Before the extreme pressure lubrication conditions are reached, hydrocarbons or other organic components constituting the lubricating oil composition are carbonized by heating and shearing before the extreme pressure lubrication conditions, forming a carbide film on the metal surface. there's a possibility that. Therefore, when the extreme pressure agent is used alone, the carbide coating inhibits the contact between the extreme pressure agent and the metal surface, and there is a possibility that the extreme pressure agent cannot be expected to have a sufficient effect.
　極圧剤は単独で添加してもよいが、本発明における電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物は共重合体といった飽和炭化水素を主成分とするため、予め使用する他の添加剤とともに、鉱物油または合成炭化水素油等の潤滑油基油に溶解させた状態で添加した方が、分散性の観点から好ましい。具体的には、極圧剤成分などの諸成分をあらかじめ配合し、更に鉱物油または合成炭化水素油等の潤滑油基油に溶解させた、いわゆる添加剤パッケージを選択して潤滑油組成物に添加する方法がより好ましい。 Although the extreme pressure agent may be added alone, the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle of the present invention is mainly composed of saturated hydrocarbons such as copolymers. From the standpoint of dispersibility, it is preferable to add it in a state dissolved in a lubricating base oil such as a mineral oil or a synthetic hydrocarbon oil together with other additives that are used in advance. Specifically, a so-called additive package, in which various components such as extreme pressure agent components are blended in advance and dissolved in a lubricating base oil such as mineral oil or synthetic hydrocarbon oil, is selected and added to the lubricating oil composition. A method of adding is more preferable.
　電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油には、自動変速機油や無段変速機油用潤滑油のために各種必要添加剤を配合し、鉱物油もしくは合成炭化水素油等の潤滑油に濃縮溶解させた、いわゆるＤＩパッケージが工業的に供給されており、例えば自動変速機油用ＤＩパッケージとしてはＡＦＴＯＮ ＣＨＥＭＩＣＡＬ社製ＨＩＴＥＣ３４１９Ｄ、ＡＦＴＯＮ ＣＨＥＭＩＣＡＬ社製ＨＩＴＥＣ２４２６等が挙げられ、無段変速機油用ＤＩパッケージとしてはＬＵＢＲＩＺＯＬ社製Ｌｕｂｒｉｚｏｌ６３７３等が挙げられるが、これらのＤＩパッケージを本発明の潤滑油組成物に適用することもできる。 Lubricating oils used for cooling electric motors and lubricating gears in electric vehicles contain various necessary additives for lubricating oils for automatic transmission oils and continuously variable transmission oils, and are either mineral oils or synthetic hydrocarbon oils. A so-called DI package, which is concentrated and dissolved in a lubricating oil such as a lubricating oil, is industrially supplied. Examples of DI packages for machine oils include Lubrizol 6373 manufactured by LUBRIZOL, and these DI packages can also be applied to the lubricating oil composition of the present invention.
　極圧剤は、必要に応じて潤滑油組成物１００質量％に対して０～１０質量％の範囲で用いられる。耐摩耗剤としては、二硫化モリブデンなどの無機または有機モリブデン化合物、グラファイト、硫化アンチモン、ポリテトラフルオロエチレンなどを例示することができる。耐摩耗剤は、必要に応じて潤滑油組成物１００質量％に対して０～３質量％の範囲で用いられる。 The extreme pressure agent is used in the range of 0 to 10% by mass with respect to 100% by mass of the lubricating oil composition as necessary. Examples of antiwear agents include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, and polytetrafluoroethylene. The antiwear agent is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
　摩擦調整剤としては、炭素数６～３０のアルキル基又はアルケニル基、特に炭素数６～３０の直鎖アルキル基又は直鎖アルケニル基を分子中に少なくとも１個有する、アミン化合物、イミド化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩等を例示することができる。 Friction modifiers include amine compounds, imide compounds, and fatty acids having at least one alkyl or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl or alkenyl group having 6 to 30 carbon atoms in the molecule. Examples include esters, fatty acid amides, fatty acid metal salts, and the like.
　アミン化合物としては、炭素数６～３０の直鎖状若しくは分枝状、好ましくは直鎖状の脂肪族モノアミン、直鎖状若しくは分枝状、好ましくは直鎖状の脂肪族ポリアミン、又はこれら脂肪族アミンのアルキレンオキシド付加物等が例示できる。イミド化合物としては、炭素数６～３０の直鎖状若しくは分岐状のアルキル基又はアルケニル基を有するコハク酸イミド及び／又はそのカルボン酸、ホウ酸、リン酸、硫酸等による変性化合物等が挙げられる。脂肪酸エステルとしては、炭素数７～３１の直鎖状又は分枝状、好ましくは直鎖状の脂肪酸と、脂肪族１価アルコール又は脂肪族多価アルコールとのエステル等が例示できる。脂肪酸アミドとしては、炭素数７～３１の直鎖状又は分枝状、好ましくは直鎖状の脂肪酸と、脂肪族モノアミン又は脂肪族ポリアミンとのアミド等が例示できる。脂肪酸金属塩としては、炭素数７～３１の直鎖状又は分枝状、好ましくは直鎖状の脂肪酸の、アルカリ土類金属塩（マグネシウム塩、カルシウム塩等）や亜鉛塩等が挙げられる。 As the amine compound, linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or these aliphatic Alkylene oxide adducts of group amines and the like can be exemplified. Examples of the imide compound include succinimide having a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms and/or modified compounds thereof with carboxylic acid, boric acid, phosphoric acid, sulfuric acid, etc. . Examples of fatty acid esters include esters of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of fatty acid amides include amides of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms and aliphatic monoamines or aliphatic polyamines. Examples of fatty acid metal salts include alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms.
　摩擦調整剤は、必要に応じて潤滑油組成物１００質量％に対して０．０１～５．０質量％の範囲で用いられる。 The friction modifier is used in the range of 0.01 to 5.0% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
　清浄分散剤としては、金属スルホネート、金属フェネート、金属フォスファネート、コハク酸イミドなどを例示することができる。清浄分散剤は、必要に応じて潤滑油組成物１００質量％に対して０～１５質量％の範囲で用いられる。 Examples of detergent-dispersants include metal sulfonates, metal phenates, metal phosphanates, and succinimides. Detergency-dispersants are used in the range of 0 to 15% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
　粘度指数向上剤としては、エチレン－α－オレフィン共重合体（（Ｃ）エチレン－α－オレフィン共重合体を除く。）の他に、分子量が５０，０００を超えるようなオレフィンコポリマー、メタクリレート系共重合体、液状ポリブテン、１００℃動粘度１５ｍｍ2／ｓ以上のポリ－α－オレフィン等の既知の粘度指数向上剤を併用することができる。粘度指数向上剤は、必要に応じて潤滑油組成物１００質量％に対して０～１０質量％の範囲で用いられる。 Viscosity index improvers include ethylene-α-olefin copolymers (excluding (C) ethylene-α-olefin copolymers), olefin copolymers with a molecular weight exceeding 50,000, and methacrylate-based copolymers. Known viscosity index improvers such as polymers, liquid polybutene, and poly-α-olefins having a kinematic viscosity of 15 mm 2 /s or more at 100° C. can be used in combination. A viscosity index improver is used in the range of 0 to 10% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
　酸化防止剤としては、２,６－ジ－ｔ－ブチル－４－メチルフェノールなどのフェノール系やアミン系の化合物が挙げられる。酸化防止剤は、必要に応じて潤滑油組成物１００質量％に対して０～３質量％の範囲で用いられる。 Antioxidants include phenolic and amine compounds such as 2,6-di-t-butyl-4-methylphenol. Antioxidants are used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition as necessary.
　腐食防止剤としては、ベンゾトリアゾール、ベンゾイミダゾール、チアジアゾール等の化合物が挙げられる。腐食防止剤は、必要に応じて潤滑油組成物１００質量％に対して０～３質量％の範囲で用いられる。 Corrosion inhibitors include compounds such as benzotriazole, benzimidazole, and thiadiazole. Corrosion inhibitors are optionally used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition.
　防錆剤としては、各種アミン化合物、カルボン酸金属塩、多価アルコールエステル、リン化合物、スルホネートなどの化合物が挙げられる。防錆剤は、必要に応じて潤滑油組成物１００質量％に対して０～３質量％の範囲で用いられる。 Examples of rust preventives include compounds such as various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, and sulfonates. The antirust agent is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
　消泡剤としては、ジメチルシロキサン、シリカゲル分散体などのシリコーン系化合物、アルコール系またはエステル系の化合物などを例示することができる。消泡剤は、必要に応じて潤滑油組成物１００質量％に対して０～０．２質量％の範囲で用いられる。 Examples of antifoaming agents include silicone-based compounds such as dimethylsiloxane and silica gel dispersions, and alcohol-based or ester-based compounds. Antifoaming agents are used in the range of 0 to 0.2% by mass with respect to 100% by mass of the lubricating oil composition, if necessary.
　流動点降下剤としては、種々公知の流動点降下剤を使用し得る。具体的には、有機酸エステル基を含有する高分子化合物が用いられ、有機酸エステル基を含有するビニル重合体が特に好適に用いられる。有機酸エステル基を含有するビニル重合体としては例えばメタクリル酸アルキルの（共）重合体、アクリル酸アルキルの（共）重合体、フマル酸アルキルの（共）重合体、マレイン酸アルキルの（共）重合体、アルキル化ナフタレン等が挙げられ、好ましくはアクリル酸アルキルの（共）重合体であり、より好ましくは炭素数が１～１０個のアルコールとアクリル酸のエステル化合物であるアクリル酸アルキルの（共）重合体である。 Various known pour point depressants can be used as the pour point depressant. Specifically, a polymer compound containing an organic acid ester group is used, and a vinyl polymer containing an organic acid ester group is particularly preferably used. Vinyl polymers containing an organic acid ester group include, for example, alkyl methacrylate (co)polymers, alkyl acrylate (co)polymers, alkyl fumarate (co)polymers, and alkyl maleate (co)polymers. Examples include polymers, alkylated naphthalenes, etc., preferably (co)polymers of alkyl acrylates, more preferably (co)polymers of alkyl acrylates ( co) polymer.
　このような流動点降下剤は、融点が－１３℃以下であり、好ましくは－１５℃、さらに好ましくは－１７℃以下である。流動点降下剤の融点は、示差走査熱量計（ＤＳＣ）を用いて測定される。具体的には、試料約５ｍｇをアルミパンに詰めて２００℃まで昇温し、２００℃で５分間保持した後、１０℃／分で－４０℃まで冷却し、－４０℃で５分保持した後、１０℃／分で昇温する際の吸熱曲線から求める。 Such a pour point depressant has a melting point of -13°C or lower, preferably -15°C or lower, more preferably -17°C or lower. The melting point of pour point depressants is measured using a differential scanning calorimeter (DSC). Specifically, about 5 mg of the sample was packed in an aluminum pan, heated to 200 ° C., held at 200 ° C. for 5 minutes, cooled to -40 ° C. at 10 ° C./min, and held at -40 ° C. for 5 minutes. After that, it is obtained from the endothermic curve when the temperature is raised at 10°C/min.
　上記流動点降下剤はさらに、ゲルパーミエーションクロマトグラフィーによって得られるポリスチレン換算重量平均分子量が２０,０００～４００,０００の範囲にあり、好ましくは３０,０００～３００,０００、より好ましくは４０,０００～２００,０００の範囲にある。 The pour point depressant further has a polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography in the range of 20,000 to 400,000, preferably 30,000 to 300,000, more preferably 40,000. ~200,000.
　流動点降下剤は、必要に応じて潤滑油組成物１００質量％に対して０～２質量％、好ましくは０．０１～１質量％、より好ましくは０．０２～０．４質量％、さらに好ましくは０．０５～０．３５質量％の範囲で用いられる。流動点降下剤の添加量が上記範囲を上回ると、潤滑油組成物の剪断安定性が低下し、低粘度化によって潤滑性が悪化する恐れがある。また流動点降下能も損なうおそれがある。 The pour point depressant is optionally 0 to 2% by mass, preferably 0.01 to 1% by mass, more preferably 0.02 to 0.4% by mass, based on 100% by mass of the lubricating oil composition, and further It is preferably used in the range of 0.05 to 0.35% by mass. If the amount of the pour point depressant added exceeds the above range, the shear stability of the lubricating oil composition may decrease, and lubricity may deteriorate due to the low viscosity. Moreover, the pour point depressing ability may also be impaired.
　上記の添加剤以外にも、抗乳化剤、着色剤、油性剤（油性向上剤）などを必要に応じて用いることができる。 In addition to the above additives, demulsifiers, colorants, oiliness agents (oiliness improvers), etc. can be used as necessary.
　電動車両では、自動変速機油や無段変速機油において用いられる、各種必要添加剤を配合し、鉱物油もしくは合成炭化水素油等の潤滑油に濃縮溶解させた、いわゆるＤＩパッケージを使用する場合もある。ＤＩパッケージは工業的に供給されており、例えば自動変速機油用ＤＩパッケージとしてはＡＦＴＯＮ ＣＨＥＭＩＣＡＬ社製ＨＩＴＥＣ３４１９Ｄ、ＡＦＴＯＮ ＣＨＥＭＩＣＡＬ社製ＨＩＴＥＣ２４２６等が挙げられ、無段変速機油用ＤＩパッケージとしてはＬＵＢＲＩＺＯＬ社製Ｌｕｂｒｉｚｏｌ６３７３等が挙げられるが、これらのＤＩパッケージを本発明の潤滑油組成物に適用することもできる。 Electric vehicles sometimes use a so-called DI package, in which various necessary additives used in automatic transmission oil and continuously variable transmission oil are blended and concentrated and dissolved in lubricating oil such as mineral oil or synthetic hydrocarbon oil. . DI packages are industrially supplied. For example, DI packages for automatic transmission oils include HITEC3419D manufactured by AFTON CHEMICAL and HITEC2426 manufactured by AFTON CHEMICAL, and DI packages for continuously variable transmission oils include Lubrizol6373 manufactured by LUBRIZOL. but these DI packages can also be applied to the lubricating oil composition of the present invention.
　＜用途＞
　本発明の潤滑油組成物は、例えば、電気自動車、プラグインハイブリッド車、ハイブリッド車、燃料電池車のような電動車両に搭載された電動モーターの冷却および歯車の潤滑のために用いることができ、同一の潤滑油基油を含む従来の潤滑油に比べて極めて優れた温度粘度特性、すなわち高温での油膜保持性および低温粘度特性を有し、電動車両の省エネルギー化に大きく寄与できる。電動車両としては、歯車と電動モーターとの距離が短い、すなわち高い放熱性が求められるインホイールモーターが装備された電動車両において特に有用である。また電動車両としては、高い潤滑性によって滑らかな走行が求められる要介護者向けの電動車いすや電動カートにおいても特に有用である。更に高い出力が瞬間的に求められる電動スケートボード、電動ローラースケートにおいても放熱性が求められるため特に有用である。また、剪断安定性に優れるため電動車両の長時間使用における潤滑性能を維持し、システムの性能維持に寄与する。加えて本発明の潤滑油組成物は放熱性能が極めて優れているため、電動車両のギアやベアリングの潤滑性能のみならず高い電動モーター冷却性能を有する。本発明の潤滑油組成物電動車両における電動モーターの冷却および歯車の潤滑に極めて有用ある。 <Application>
The lubricating oil composition of the present invention can be used, for example, for cooling electric motors and lubricating gears mounted in electric vehicles such as electric vehicles, plug-in hybrid vehicles, hybrid vehicles, and fuel cell vehicles. Compared to conventional lubricating oils containing the same lubricating base oil, the lubricating oil has extremely excellent temperature-viscosity properties, that is, oil film retention at high temperatures and low-temperature viscosity properties, and can greatly contribute to the energy saving of electric vehicles. As an electric vehicle, the distance between the gear and the electric motor is short, that is, it is particularly useful for an electric vehicle equipped with an in-wheel motor that requires high heat dissipation. As an electric vehicle, it is particularly useful in electric wheelchairs and electric carts for people requiring nursing care, which require smooth running due to high lubricity. Furthermore, it is particularly useful for electric skateboards and electric roller skates, which require high output instantaneously, because heat dissipation is required. In addition, because of its excellent shear stability, it maintains lubricating performance even when an electric vehicle is used for a long time, contributing to maintenance of system performance. In addition, since the lubricating oil composition of the present invention has extremely excellent heat dissipation performance, it has not only lubricating performance for gears and bearings of electric vehicles but also high cooling performance for electric motors. The lubricating oil composition of the present invention is extremely useful for cooling electric motors and lubricating gears in electric vehicles.
　以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
　［評価方法］
　下記実施例および比較例等において、エチレン－α－オレフィン共重合体および潤滑油組成物の物性等は以下の方法で測定した。 [Evaluation method]
In the following examples, comparative examples, etc., the physical properties of the ethylene-α-olefin copolymers and lubricating oil compositions were measured by the following methods.
　＜エチレンモル含有率（ｍｏｌ％）＞
　日本分光社製フーリエ変換赤外分光光度計ＦＴ／ＩＲ－６１０またはＦＴ／ＩＲ－６１００を用い、長鎖メチレン基の横揺れ振動に基づく７２１ｃｍ-1付近の吸収とプロピレンの骨格振動に基づく１１５５ｃｍ-1付近の吸収との吸光度比（Ｄ１１５５ｃｍ-1／Ｄ７２１ｃｍ-1）を算出し、予め作成しておいた検量線（ＡＳＴＭ Ｄ３９００での標準試料を使って作成）よりエチレン含有率（重量％）を求めた。次に、得られたエチレン含有率（エチレン重量含有率（重量％））を用い、下記式に従ってエチレン含有率（エチレンモル含有率（ｍｏｌ％））を求めた。 <Ethylene molar content (mol%)>
Using a Fourier transform infrared spectrophotometer FT/IR-610 or FT/IR-6100 manufactured by JASCO Corporation, absorption near 721 cm -1 based on the horizontal vibration of long-chain methylene groups and 1155 cm - based on the skeletal vibration of propylene were measured. The absorbance ratio (D1155 cm -1 /D721 cm -1 ) to the absorption near 1 was calculated, and the ethylene content (% by weight) was calculated from a previously prepared calibration curve (prepared using a standard sample according to ASTM D3900). asked. Next, using the obtained ethylene content (ethylene weight content (% by weight)), the ethylene content (ethylene molar content (mol%)) was determined according to the following formula.
Figure JPOXMLDOC01-appb-M000013
 　＜動粘度および粘度指数＞
１００℃動粘度、４０℃動粘度、および粘度指数は、ＪＩＳ Ｋ２２８３に記載の方法により、測定した。
Figure JPOXMLDOC01-appb-M000013
 <Kinematic viscosity and viscosity index>
100° C. kinematic viscosity, 40° C. kinematic viscosity, and viscosity index were measured by the method described in JIS K2283.
　＜重量平均分子量（Ｍｗ），分子量分布（Ｍｗ／Ｍｎ）＞
　分子量分布は、東ソー株式会社ＨＬＣ－８３２０ＧＰＣを用いて以下のようにして測定した。分離カラムとして、ＴＳＫｇｅｌ　ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ－Ｍ（４本）を用い、カラム温度を４０℃とし、移動相にはテトラヒドロフラン（和光純薬社製）を用い、展開速度を０．３５ｍｌ／分とし、試料濃度を５．５ｇ/Ｌとし、試料注入量を２０マイクロリットルとし、検出器として示差屈折計を用いた。標準ポリスチレンとしては、東ソー社製（ＰＳｔＱｕｉｃｋ ＭＰ－Ｍ）のものを用いた。汎用校正の手順に従い、ポリスチレン分子量換算として重量平均分子量（Ｍｗ）並びに数平均分子量（Ｍｎ）を算出し、これらの値から分子量分布（Ｍｗ／Ｍｎ）を算出した。 <Weight average molecular weight (Mw), molecular weight distribution (Mw/Mn)>
Molecular weight distribution was measured as follows using Tosoh Corporation HLC-8320GPC. As the separation column, TSKgel SuperMultiporeHZ-M (4 columns) was used, the column temperature was set to 40 ° C., tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the development rate was set to 0.35 ml / min, and the sample concentration was set to The concentration was 5.5 g/L, the sample injection amount was 20 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, one manufactured by Tosoh Corporation (PStQuick MP-M) was used. The weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight according to the general-purpose calibration procedure, and the molecular weight distribution (Mw/Mn) was calculated from these values.
　＜ハーゼン色度＞
　ＪＩＳ　Ｋ００７１に記載の方法に従い、ＡＰＨＡ値を求めた。 <Hazen Chromaticity>
The APHA value was obtained according to the method described in JIS K0071.
　＜Ｂ値＞
　ｏ－ジクロロベンゼン／ベンゼン－ｄ6（４／１［ｖｏｌ／ｖｏｌ％］）を測定溶媒とし、測定温度１２０℃、スペクトル幅２５０ｐｐｍ、パルス繰り返し時間５．５秒、かつパルス幅４．７μ秒（４５°パルス）の測定条件下（１００ＭＨｚ、日本電子ＥＣＸ４００Ｐ）、または測定温度１２０℃、スペクトル幅２５０ｐｐｍ、パルス繰り返し時間５．５秒、かつパルス幅５．０μ秒（４５°パルス）の測定条件下（１２５ ＭＨｚ、ブルカー・バイオスピンＡＶＡＮＣＥＩＩＩｃｒｙｏ－５００）にて13Ｃ－ＮＭＲスペクトルを測定し、下記式［１］に基づきＢ値を算出した。ピークの帰属は前述の公知文献を参考にして行った。 <B value>
o-Dichlorobenzene/benzene-d 6 (4/1 [vol/vol%]) was used as the measurement solvent, the measurement temperature was 120°C, the spectrum width was 250 ppm, the pulse repetition time was 5.5 seconds, and the pulse width was 4.7 μs ( 45 ° pulse) measurement conditions (100 MHz, JEOL ECX400P), or measurement temperature 120 ° C, spectrum width 250 ppm, pulse repetition time 5.5 seconds, and pulse width 5.0 μs (45 ° pulse) measurement conditions 13 C-NMR spectrum was measured at (125 MHz, Bruker Biospin AVANCE IIIcryo-500), and the B value was calculated based on the following formula [1]. Attribution of peaks was performed with reference to the above-mentioned known literature.
Figure JPOXMLDOC01-appb-M000014
 　式［１］中、ＰEはエチレン成分の含有モル分率を示し、ＰOはα－オレフィン成分の含有モル分率を示し、ＰOEは全ｄｙａｄ連鎖のエチレン－α－オレフィン連鎖のモル分率を示す。
Figure JPOXMLDOC01-appb-M000014
 In formula [1], P E represents the molar fraction of the ethylene component, PO represents the molar fraction of the α-olefin component, and P OE represents the molar fraction of the ethylene-α-olefin chains of all the dyad chains. rate.
　＜熱拡散率＞
　熱拡散率は、潤滑油組成物の熱伝導率、比熱、密度をそれぞれ求めることで以下の式で表される。 <Thermal diffusivity>
The thermal diffusivity is expressed by the following formula by determining the thermal conductivity, specific heat, and density of the lubricating oil composition.
Figure JPOXMLDOC01-appb-M000015
 　熱伝導率は、ＪＩＳ　Ｒ２６１６に準拠し試験温度５０℃において測定した。比熱は、真空理工製比熱測定装置ＳＨ－３０００型を用い、空気雰囲気下において３０℃から８０℃の間において断熱条件において連続で測定し、５０℃における比熱を採用した。密度は、ＪＩＳ　Ｋ２２４９に準拠し５０℃において測定した。
Figure JPOXMLDOC01-appb-M000015
 Thermal conductivity was measured at a test temperature of 50° C. in accordance with JIS R2616. The specific heat was measured continuously under adiabatic conditions between 30°C and 80°C in an air atmosphere using a specific heat measuring device SH-3000 manufactured by SHINKU RIKO, and the specific heat at 50°C was adopted. Density was measured at 50° C. in accordance with JIS K2249.
　＜体積抵抗率＞
　体積抵抗率は、ＪＩＳ　Ｃ２１０１に準拠し、試験温度５０℃、２５０Ｖにおいて測定した。 <Volume resistivity>
The volume resistivity was measured at a test temperature of 50° C. and 250 V according to JIS C2101.
　＜比誘電率＞
　比誘電率は、ＪＩＳ　Ｃ２１３８に準拠し、試験温度５０℃において測定した。 <Dielectric constant>
The dielectric constant was measured at a test temperature of 50°C in accordance with JIS C2138.
　＜融点＞
　セイコーインスツルメント社Ｘ－ＤＳＣ－７０００を用い、簡易密閉できるアルミサンプルパンに約８ｍｇのエチレン－α－オレフィン共重合体を入れてＤＳＣセルに配置し、ＤＳＣセルを窒素雰囲気下にて室温から１５０℃まで１０℃／分で昇温し、次いで、１５０℃で５分間保持した後、１０℃／分で降温し、ＤＳＣセルを－１００℃まで冷却した（降温過程）。次いで、１００℃で５分間保持した後、１０℃／分で昇温し、昇温過程で得られるエンタルピー曲線が極大値を示す温度を融点（Ｔｍ）とし、融解に伴う吸熱量の総和を融解熱量（ΔＨ）とした。ピークが観測されないか、融解熱量（ΔＨ）の値が１Ｊ／ｇ以下の場合、融点（Ｔｍ）なしとみなした。融点（Ｔｍ）、および融解熱量（ΔＨ）の求め方はＪＩＳ Ｋ７１２１に基づいて行った。 <Melting point>
Using Seiko Instruments X-DSC-7000, put about 8 mg of ethylene-α-olefin copolymer in an aluminum sample pan that can be easily sealed and place it in the DSC cell. The temperature was raised to 150° C. at 10° C./min, then held at 150° C. for 5 minutes, and then lowered at 10° C./min to cool the DSC cell to −100° C. (temperature drop process). Next, after holding at 100° C. for 5 minutes, the temperature is raised at 10° C./min. The temperature at which the enthalpy curve obtained in the heating process shows the maximum value is defined as the melting point (Tm), and the sum of the endothermic amounts accompanying melting is the melting point. It was taken as the amount of heat (ΔH). If no peak was observed or if the heat of fusion (ΔH) value was 1 J/g or less, it was considered as having no melting point (Tm). The melting point (Tm) and heat of fusion (ΔH) were determined according to JIS K7121.
　＜塩素含有量＞
　塩素含有量は、サーモフィッシャーサイエンティフィック社ＩＣＳ－１６００を用い、エチレン－α－オレフィン共重合体を、試料ボートに入れてＡｒ／Ｏ2気流中、燃焼炉設定温度９００℃にて燃焼分解した。このときの発生ガスを吸収液に吸収させ、イオンクロマトグラフ法にて定量した。 <Chlorine content>
Chlorine content was determined by using ICS-1600 from Thermo Fisher Scientific Co., Ltd., and ethylene-α-olefin copolymer was placed in a sample boat and burned and decomposed in an Ar/O 2 stream at a combustion furnace setting temperature of 900°C. . The generated gas at this time was absorbed into the absorbent and quantified by ion chromatography.
　＜流動点＞
　流動点はＡＳＴＭ　Ｄ９７に記載の方法により測定した。なお、流動点が－５０℃を下回る場合は、＜－５０と記載した。 <Pour point>
Pour point was measured by the method described in ASTM D97. If the pour point is lower than -50°C, it is indicated as <-50.
　＜低温粘度＞
　低温粘度は、ＡＳＴＭ　Ｄ６８２１に記載の方法により、－４０℃における粘度を測定した。 <Low temperature viscosity>
Low-temperature viscosity was measured at -40°C by the method described in ASTM D6821.
　＜剪断安定性＞
　潤滑油組成物に対して、自動変速機油剪断安定性試験方法であるＪＡＳＯ　Ｍ３４７に準拠し、６０分の超音波照射を行い、下式で表される照射による１００℃での動粘度の低下率（剪断試験後粘度低下率）を評価した。 <Shear stability>
The lubricating oil composition was subjected to ultrasonic irradiation for 60 minutes in accordance with JASO M347, which is an automatic transmission oil shear stability test method, and the reduction rate of kinematic viscosity at 100 ° C. due to irradiation represented by the following formula. (Viscosity reduction rate after shear test) was evaluated.
Figure JPOXMLDOC01-appb-M000016
 　［エチレン－α－オレフィン共重合体（Ｂ）の製造］
　エチレン－α－オレフィン共重合体（Ｂ）は以下の重合例に従い製造した。なお、得られたエチレン－α－オレフィン共重合体（Ｂ）について、必要に応じて、下記方法で水添操作を実施した。
Figure JPOXMLDOC01-appb-M000016
 [Production of ethylene-α-olefin copolymer (B)]
Ethylene-α-olefin copolymer (B) was produced according to the following polymerization examples. The obtained ethylene-α-olefin copolymer (B) was hydrogenated by the following method, if necessary.
　＜水添操作＞
　内容積１Ｌのステンレス製オートクレーブに０．５質量％Ｐｄ／アルミナ触媒のヘキサン溶液１００ｍＬおよびエチレン－α－オレフィン共重合体の３０質量％ヘキサン溶液５００ｍＬを加え、オートクレーブを密閉した後、窒素置換を行なった。次いで、撹拌をしながら１４０℃まで昇温し、系内を水素置換した後、水素で１．５ＭＰａまで昇圧して１５分間水添反応を実施した。 <Hydrogenation operation>
100 mL of a hexane solution of 0.5% by mass Pd/alumina catalyst and 500 mL of a 30% by mass hexane solution of an ethylene-α-olefin copolymer were added to a 1 L stainless steel autoclave, and the autoclave was sealed and then purged with nitrogen. Ta. Then, the temperature was raised to 140° C. with stirring, and after the inside of the system was replaced with hydrogen, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.
　＜メタロセン化合物の合成＞
　〔合成例１〕
　［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリドの合成
　（ｉ）６－メチル－６－フェニルフルベンの合成
　窒素雰囲気下、２００ｍＬ三口フラスコにリチウムシクロペンタジエン７．３ｇ （１０１．６ｍｍｏｌ）および脱水テトラヒドロフラン１００ｍＬを加えて攪拌した。溶液をアイスバスで冷却し、アセトフェノン１５．０ｇ（１１１．８ｍｍｏｌ）を滴下した。その後、室温で２０時間攪拌し、得られた溶液を希塩酸水溶液でクエンチした。ヘキサン１００ｍＬを加えて可溶分を抽出し、この有機層を水、飽和食塩水で洗浄後、無水硫酸マグネシウムで乾燥した。その後、溶媒を留去し、得られた粘性液体をカラムクロマトグラフィー（ヘキサン）で分離し、目的物（赤色粘性液体）を得た。 <Synthesis of Metallocene Compound>
[Synthesis Example 1]
Synthesis of [methylphenylmethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride (i) Synthesis of 6-methyl-6-phenylfulvene Nitrogen atmosphere Then, 7.3 g (101.6 mmol) of lithium cyclopentadiene and 100 mL of dehydrated tetrahydrofuran were added to a 200 mL three-necked flask and stirred. The solution was cooled with an ice bath and 15.0 g (111.8 mmol) of acetophenone was added dropwise. After stirring at room temperature for 20 hours, the resulting solution was quenched with dilute aqueous hydrochloric acid. 100 mL of hexane was added to extract the soluble matter, and the organic layer was washed with water and saturated brine and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off, and the resulting viscous liquid was separated by column chromatography (hexane) to obtain the desired product (red viscous liquid).
　（ｉｉ）メチル（シクロペンタジエニル）（２，７－ジ－ｔ－ブチルフルオレニル）（フェニル）メタンの合成
　窒素雰囲気下、１００ｍＬ三口フラスコに２，７－ジ－ｔ－ブチルフルオレン２．０１ｇ（７．２０ｍｍｏｌ）および脱水ｔ－ブチルメチルエーテル５０ｍＬを添加した。氷浴で冷却しながらｎ－ブチルリチウム/ヘキサン溶液（１．６５Ｍ）４．６０ｍＬ（７．５９ｍｍｏｌ）を徐々に添加し、室温で１６時間攪拌した。６－メチル－６－フェニルフルベン１．６６ｇ（９．８５ｍｍｏｌ）を添加した後、加熱還流下で１時間攪拌した。氷浴で冷却しながら水５０ｍＬを徐々に添加し、得られた二層の溶液を２００ｍＬ分液漏斗に移した。ジエチルエーテル５０ｍＬを加えて数回振った後水層を除き、有機層を水５０ｍＬで３回、飽和食塩水５０ｍＬで１回洗浄した。無水硫酸マグネシウムで３０分間乾燥した後、減圧下で溶媒を留去した。少量のヘキサンを加えて得た溶液に超音波を当てたところ固体が析出したので、これを採取して少量のヘキサンで洗浄した。減圧下で乾燥し、白色固体としてメチル（シクロペンタジエニル）（２，７－ジ－ｔ－ブチルフルオレニル）（フェニル）メタン２．８３ｇを得た。 (ii) Synthesis of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane 2,7-di-t-butylfluorene2. 01 g (7.20 mmol) and 50 mL of dry t-butyl methyl ether were added. 4.60 mL (7.59 mmol) of n-butyllithium/hexane solution (1.65 M) was gradually added while cooling with an ice bath, and the mixture was stirred at room temperature for 16 hours. After adding 1.66 g (9.85 mmol) of 6-methyl-6-phenylfulvene, the mixture was stirred under reflux with heating for 1 hour. 50 mL of water was slowly added with ice bath cooling and the resulting biphasic solution was transferred to a 200 mL separatory funnel. After adding 50 mL of diethyl ether and shaking several times, the aqueous layer was removed, and the organic layer was washed three times with 50 mL of water and once with 50 mL of saturated brine. After drying with anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. When ultrasonic waves were applied to a solution obtained by adding a small amount of hexane, a solid precipitated, which was collected and washed with a small amount of hexane. Drying under reduced pressure gave 2.83 g of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane as a white solid.
　（ｉｉｉ）［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリドの合成
　窒素雰囲気下、１００ｍＬシュレンク管にメチル（シクロペンタジエニル）（２，７－ジ－ｔ－ブチルフルオレニル）（フェニル）メタン１．５０ｇ（３．３６ｍｍｏｌ）、脱水トルエン５０ｍＬおよびＴＨＦ ５７０μＬ（７．０３ｍｍｏｌ）を順次添加した。氷浴で冷却しながらｎ－ブチルリチウム／ヘキサン溶液（１．６５Ｍ）４．２０ｍＬ（６．９３ｍｍｏｌ）を徐々に添加し、４５℃で５時間攪拌した。減圧下で溶媒を留去し、脱水ジエチルエーテル４０ｍＬを添加して赤色溶液とした。メタノール／ドライアイス浴で冷却しながら四塩化ジルコニウム ７２８ｍｇ（３．１２ｍｍｏｌ）を添加し、室温まで徐々に昇温しながら１６時間攪拌したところ、赤橙色スラリーが得られた。減圧下で溶媒を留去して得られた固体をグローブボックス内に持ち込み、ヘキサンで洗浄した後、ジクロロメタンで抽出した。減圧下で溶媒を留去して濃縮した後、少量のヘキサンを加え、－２０℃で放置したところ赤橙色固体が析出した。この固体を少量のヘキサンで洗浄した後、減圧下で乾燥することにより、赤橙色固体として［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド１．２０ｇを得た。 (iii) Synthesis of [methylphenylmethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride Methyl (cyclopentadienyl) was added to a 100 mL Schlenk tube under a nitrogen atmosphere. Dienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane 1.50 g (3.36 mmol), dehydrated toluene 50 mL and THF 570 μL (7.03 mmol) were sequentially added. 4.20 mL (6.93 mmol) of n-butyllithium/hexane solution (1.65 M) was gradually added while cooling with an ice bath, and the mixture was stirred at 45° C. for 5 hours. The solvent was distilled off under reduced pressure, and 40 mL of dehydrated diethyl ether was added to give a red solution. While cooling in a methanol/dry ice bath, 728 mg (3.12 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature to obtain a reddish-orange slurry. The solid obtained by evaporating the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After concentrating by distilling off the solvent under reduced pressure, a small amount of hexane was added, and the mixture was allowed to stand at -20°C to precipitate a reddish orange solid. This solid was washed with a small amount of hexane and then dried under reduced pressure to obtain [methylphenylmethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylphenyl) as a reddish-orange solid. 1.20 g of olenyl)]zirconium dichloride are obtained.
　〔合成例２〕
　［エチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリドの合成
　［エチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリドは、特許第４３６７６８７号公報に記載の方法で合成した。 [Synthesis Example 2]
Synthesis of [ethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride [ethylene (η 5 -cyclopentadienyl) (η 5 -2, 7-Di-t-butylfluorenyl)]zirconium dichloride was synthesized by the method described in Japanese Patent No. 4,367,687.
　＜重合例１＞
　充分に窒素置換した内容積２Ｌのステンレス製オートクレーブにヘプタン９１０ｍＬおよびプロピレン４５ｇを装入し、系内の温度を１３０℃に昇温した後、水素２．２４ＭＰａ、エチレン０．０９ＭＰａを供給することにより全圧を３ＭＰａＧとした。次にトリイソブチルアルミニウム０．４ｍｍｏｌ、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド０．０００６ｍｍｏｌおよびN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート０．００６ｍｍｏｌを窒素で圧入し、攪拌回転数を４００ｒｐｍにすることにより重合を開始した。その後、エチレンのみを連続的に供給することにより全圧を３ＭＰａＧに保ち、１３０℃で５分間重合を行った。少量のエタノールを系内に添加することにより重合を停止した後、未反応のエチレン、プロピレン、水素をパージした。得られたポリマー溶液を、０．２ｍｏｌ／ｌの塩酸１０００ｍＬで３回、次いで蒸留水１０００ｍＬで３回洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。得られたポリマーを８０℃の減圧下で一晩乾燥し、エチレン－プロピレン共重合体２２．２ｇを得た。さらに、このエチレン－プロピレン共重合体に対して水添操作を施し、重合体１を得た。 <Polymerization Example 1>
910 mL of heptane and 45 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L that was sufficiently nitrogen-substituted, and the temperature in the system was raised to 130 ° C., and then 2.24 MPa of hydrogen and 0.09 MPa of ethylene were supplied. The total pressure was 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 0.0006 mmol of [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride and N,N- Polymerization was initiated by injecting 0.006 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate with nitrogen and setting the stirring rotation speed to 400 rpm. Thereafter, only ethylene was continuously supplied to keep the total pressure at 3 MPaG, and polymerization was carried out at 130° C. for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene and hydrogen were purged. The resulting polymer solution was washed with 1000 mL of 0.2 mol/l hydrochloric acid three times and then with 1000 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight under reduced pressure at 80° C. to obtain 22.2 g of an ethylene-propylene copolymer. Further, this ethylene-propylene copolymer was subjected to a hydrogenation operation to obtain a polymer 1.
　＜重合例２＞
　充分に窒素置換した内容積２Ｌのステンレス製オートクレーブにヘプタン７７０ｍＬおよびプロピレン１３０ｇを装入し、系内の温度を１５０℃に昇温した後、水素０．９５ＭＰａ、エチレン０．１８ＭＰａを供給することにより全圧を３ＭＰａＧとした。次にトリイソブチルアルミニウム０．４ｍｍｏｌ、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド０．０００２ｍｍｏｌおよびN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート０．００２ｍｍｏｌを窒素で圧入し、攪拌回転数を４００ｒｐｍにすることにより重合を開始した。その後、エチレンのみを連続的に供給することにより全圧を３ＭＰａＧに保ち、１５０℃で５分間重合を行った。少量のエタノールを系内に添加することにより重合を停止した後、未反応のエチレン、プロピレン、水素をパージした。得られたポリマー溶液を、０．２ｍｏｌ／ｌの塩酸１０００ｍＬで３回、次いで蒸留水１０００ｍＬで３回洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。得られたポリマーを８０℃の減圧下で一晩乾燥し、エチレン－プロピレン共重合体３４．２ｇを得た。さらに、このエチレン－プロピレン共重合体に対して水添操作を施し、重合体２を得た。 <Polymerization Example 2>
770 mL of heptane and 130 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L that was sufficiently nitrogen-substituted, and the temperature in the system was raised to 150° C., and then 0.95 MPa of hydrogen and 0.18 MPa of ethylene were supplied. The total pressure was 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 0.0002 mmol of [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride and N,N- 0.002 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate was injected with nitrogen, and polymerization was initiated by setting the rotation speed of stirring to 400 rpm. After that, only ethylene was continuously supplied to keep the total pressure at 3 MPaG, and polymerization was carried out at 150° C. for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene and hydrogen were purged. The resulting polymer solution was washed with 1000 mL of 0.2 mol/l hydrochloric acid three times and then with 1000 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight under reduced pressure at 80° C. to obtain 34.2 g of an ethylene-propylene copolymer. Furthermore, this ethylene-propylene copolymer was subjected to a hydrogenation operation to obtain a polymer 2.
　＜重合例３＞
　充分に窒素置換した内容積２Ｌのステンレス製オートクレーブにヘプタン７１０ｍＬおよびプロピレン１４５ｇを装入し、系内の温度を１５０℃に昇温した後、水素０．４０ＭＰａ、エチレン０．２７ＭＰａを供給することにより全圧を３ＭＰａＧとした。次にトリイソブチルアルミニウム０．４ｍｍｏｌ、［メチルフェニルメチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド０．０００１ｍｍｏｌおよびN,N-ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート０．００１ｍｍｏｌを窒素で圧入し、攪拌回転数を４００ｒｐｍにすることにより重合を開始した。その後、エチレンのみを連続的に供給することにより全圧を３ＭＰａＧに保ち、１５０℃で５分間重合を行った。少量のエタノールを系内に添加することにより重合を停止した後、未反応のエチレン、プロピレン、水素をパージした。得られたポリマー溶液を、０．２ｍｏｌ／ｌの塩酸１０００ｍＬで３回、次いで蒸留水１０００ｍＬで３回洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。得られたポリマーを８０℃の減圧下で一晩乾燥し、エチレン－プロピレン共重合体５２．２ｇを得た。さらに、このエチレン－プロピレン共重合体に対して水添操作を施し、重合体３を得た。 <Polymerization Example 3>
710 mL of heptane and 145 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L which had been sufficiently replaced with nitrogen, the temperature in the system was raised to 150° C., and then 0.40 MPa of hydrogen and 0.27 MPa of ethylene were supplied. The total pressure was 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 0.0001 mmol of [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-t-butylfluorenyl)]zirconium dichloride and N,N- Polymerization was initiated by injecting 0.001 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate with nitrogen and setting the stirring rotation speed to 400 rpm. After that, only ethylene was continuously supplied to keep the total pressure at 3 MPaG, and polymerization was carried out at 150° C. for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene and hydrogen were purged. The resulting polymer solution was washed with 1000 mL of 0.2 mol/l hydrochloric acid three times and then with 1000 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight under reduced pressure at 80° C. to obtain 52.2 g of an ethylene-propylene copolymer. Furthermore, this ethylene-propylene copolymer was subjected to a hydrogenation operation to obtain a polymer 3.
　＜重合例４＞
　充分に窒素置換した内容積１Ｌのガラス製重合器にヘプタン２５０ｍＬを装入し、系内の温度を５０℃に昇温した後、エチレンを２５Ｌ／ｈｒ、プロピレンを７５Ｌ／ｈｒ、水素を１００Ｌ／ｈｒの流量で連続的に重合器内に供給し、撹拌回転数６００ｒｐｍで撹拌した。次にトリイソブチルアルミニウム０．２ｍｍｏｌを重合器に装入し、次いでＭＭＡＯ０．６８８ｍｍｏｌと［エチレン（η5－シクロペンタジエニル）（η5－２，７－ジ－ｔ－ブチルフルオレニル）］ジルコニウムジクロリド０．００２３０ｍｍｏｌをトルエン中で１５分以上予備混合したものを重合器に装入することにより重合を開始した。その後、エチレン、プロピレン、水素の連続的供給を継続し、５０℃で１５分間重合を行った。少量のイソブチルアルコールを系内に添加することにより重合を停止した後、未反応のモノマーをパージした。得られたポリマー溶液を、０．２ｍｏｌ／ｌの塩酸１００ｍＬで３回、次いで蒸留水１００ｍＬで３回洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。得られたポリマーを８０℃の減圧下で一晩乾燥し、エチレン－プロピレン共重合体１．４３ｇを得た。さらに、このエチレン－プロピレン共重合体に対して水添操作を施し、重合体４を得た。 <Polymerization Example 4>
250 mL of heptane was charged into a 1-liter glass polymerization vessel that had been sufficiently purged with nitrogen, and the temperature in the system was raised to 50°C. It was continuously supplied into the polymerization vessel at a flow rate of hr and stirred at a stirring speed of 600 rpm. Next, 0.2 mmol of triisobutylaluminum was charged into the polymerization vessel, and then 0.688 mmol of MMAO and [ethylene (η 5 -cyclopentadienyl) (η 5 -2,7-di-t-butylfluorenyl)] were added. Polymerization was initiated by charging a polymerization vessel with 0.00230 mmol of zirconium dichloride premixed in toluene for 15 minutes or longer. After that, continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 50° C. for 15 minutes. After stopping the polymerization by adding a small amount of isobutyl alcohol into the system, unreacted monomer was purged. The resulting polymer solution was washed with 100 mL of 0.2 mol/l hydrochloric acid three times and then with 100 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight under reduced pressure at 80° C. to obtain 1.43 g of an ethylene-propylene copolymer. Furthermore, this ethylene-propylene copolymer was subjected to a hydrogenation operation to obtain a polymer 4.
　重合例１～重合例４にて得られたエチレン－プロピレン共重合体（それぞれ、重合体１～重合体４）と、ポリメタクリレート（ＰＭＡ）、ポリαオレフィン（ＰＡＯ）、ポリブテン（ＰＩＢ）の物性を表２に示す。 Physical properties of the ethylene-propylene copolymers obtained in Polymerization Examples 1 to 4 (polymers 1 to 4, respectively), polymethacrylate (PMA), polyαolefin (PAO), and polybutene (PIB) are shown in Table 2.
　　ポリメタクリレート（ＰＭＡ）；Ｅｖｏｎｉｋ社製Ｖｉｓｃｏｐｌｅｘ　０－２２０
　　ポリαオレフィン（ＰＡＯ）；ＥｘｘｏｎＭｏｂｉｌ　Ｃｈｅｍｉｃａｌ社製Ｓｐｅｃｔｒａｓｙｎ　ＰＡＯ－１００
　　ポリブテン（ＰＩＢ）；ＪＸ日鉱日石エネルギー社製日石ポリブテンＨＶ－１９００
　　（Ａ）鉱物油；１００℃動粘度：３．１ｍｍ2／ｓ、粘度指数：１１５、流動点：－２４℃であるＡＰＩ（Ａｍｅｒｉｃａｎ　Ｐｅｔｒｏｌｅｕｍ　Ｉｎｓｔｉｔｕｔｅ）Ｇｒｏｕｐ　ＩＩ鉱物油（ＳＫ　Ｌｕｂｒｉｃａｎｔｓ社製Ｙｕｂａｓｅ－３） Polymethacrylate (PMA); Viscoplex 0-220 from Evonik
Polyαolefin (PAO); Spectrasyn PAO-100 from ExxonMobil Chemical
Polybutene (PIB); Nisseki polybutene HV-1900 manufactured by JX Nippon Oil & Energy Corporation
(A) Mineral oil; 100° C. kinematic viscosity: 3.1 mm 2 /s, viscosity index: 115, pour point: -24° C. API (American Petroleum Institute) Group II mineral oil (SK Lubricants Yubase-3)
Figure JPOXMLDOC01-appb-T000017
 　［電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物の調製］
　電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物を調製するにあたり、上述の（Ｃ）エチレン－α－オレフィン共重合体、ＰＭＡ、ＰＡＯ、ＰＩＢ、（Ａ）鉱物油の他に以下のものを用いた。
Figure JPOXMLDOC01-appb-T000017
 [Preparation of lubricating oil composition used for cooling electric motors and lubricating gears in electric vehicles]
In preparing a lubricating oil composition used for cooling electric motors and lubricating gears in electric vehicles, the above-mentioned (C) ethylene-α-olefin copolymer, PMA, PAO, PIB, (A) mineral oil In addition to the following were used.
　　流動点降下剤；ＢＡＳＦ社製Ｉｒｇａｆｌｏｗ　７２０Ｐ
　　ＤＩパッケージ；ＡＦＴＯＮ　ＣＨＥＭＩＣＡＬ社製　ＨＩＴＥＣ　３４１９Ｄ
　＜電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物＞
　［実施例１］
　（Ａ）鉱物油と（Ｃ）エチレン－α－オレフィン共重合体として重合体１を用い、これらとＤＩパッケージと流動点降下剤とを合わせて１００質量％となるよう、ＩＳＯ４６相当粘度に電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物を配合調製した。それぞれの成分の添加量、および潤滑油組成物の物性を表３に示す。 Pour point depressant; Irgaflow 720P manufactured by BASF
DI package; HITEC 3419D manufactured by AFTON CHEMICAL
<Lubricating Oil Composition Used for Cooling Electric Motors and Lubricating Gears in Electric Vehicles>
[Example 1]
(A) Mineral oil and (C) Polymer 1 as an ethylene-α-olefin copolymer are used, and the combined amount of these, DI package, and pour point depressant is 100% by mass, and the viscosity is equivalent to ISO 46. Electric vehicle A lubricating oil composition used for cooling and lubricating gears in electric motors was formulated. Table 3 shows the amount of each component added and the physical properties of the lubricating oil composition.
　［実施例２］
　重合体１を重合体２に置き換え、各成分の添加量を表３に記載のとおり調整した以外は、実施例１と同様に潤滑油組成物を配合調製した。潤滑油組成物の物性を表３に示す。 [Example 2]
A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 2 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
　［実施例３］
　重合体１を重合体３に置き換え、各成分の添加量を表３に記載のとおり調整した以外は、実施例１と同様に潤滑油組成物を配合調製した。潤滑油組成物の物性を表３に示す。 [Example 3]
A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 3 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
　［実施例４］
　重合体１を重合体４に置き換え、各成分の添加量を表３に記載のとおり調整した以外は、実施例１と同様に潤滑油組成物を配合調製した。潤滑油組成物の物性を表３に示す。 [Example 4]
A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polymer 4 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
　［比較例１］
　重合体１をポリメタクリレート（ＰＭＡ）に置き換え、流動点降下剤を添加せず、各成分の添加量を表３に記載のとおり調整した以外は、実施例１と同様に潤滑油組成物を配合調製した。潤滑油組成物の物性を表３に示す。 [Comparative Example 1]
A lubricating oil composition was formulated in the same manner as in Example 1, except that polymer 1 was replaced with polymethacrylate (PMA), no pour point depressant was added, and the amount of each component added was adjusted as shown in Table 3. prepared. Table 3 shows the physical properties of the lubricating oil composition.
　［比較例２］
　重合体１をポリαオレフィン（ＰＡＯ）に置き換え、各成分の添加量を表３に記載のとおり調整した以外は、実施例１と同様に潤滑油組成物を配合調製した。潤滑油組成物の物性を表３に示す。 [Comparative Example 2]
A lubricating oil composition was blended and prepared in the same manner as in Example 1, except that polymer 1 was replaced with polyαolefin (PAO) and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
　［比較例３］
　重合体１をポリブテン（ＰＩＢ）に置き換え、各成分の添加量を表３に記載のとおり調整した以外は、実施例１と同様に潤滑油組成物を配合調製した。潤滑油組成物の物性を表３に示す。 [Comparative Example 3]
A lubricating oil composition was formulated in the same manner as in Example 1, except that polybutene (PIB) was substituted for polymer 1 and the amount of each component added was adjusted as shown in Table 3. Table 3 shows the physical properties of the lubricating oil composition.
Figure JPOXMLDOC01-appb-T000018
 　潤滑油基油に（Ａ）鉱物油を用いた、電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物として、（Ｃ）エチレン－α－オレフィン共重合体を含有する実施例１～３と（Ｃ）エチレン－α－オレフィン共重合体に代わりＰＭＡを含有する比較例１とを比較すると、本発明の潤滑油組成物は、剪断試験後も粘度低下が生じないことから、電動車両の機構を長期間にわたり保護し続けることができる。一方で、（Ｃ）エチレン－α－オレフィン共重合体に代わりにＰＡＯあるいはＰＩＢを含有する比較例２や比較例３の潤滑油組成物は、熱拡散率が７．０×１０-2を下回っており十分なモーター冷却性能が得られない。（Ｃ）エチレン－α－オレフィン共重合体は、メチレン連鎖を主骨格とし、ＰＡＯ、ＰＩＢと比較すると分子末端の自由度が小さいため、分子振動による発熱が抑制され、潤滑油組成物に用いた場合に優れた冷却ないし放熱性能が発揮されると考えられる。また、低温において流動性が乏しいため、低温環境下において著しく省燃費性が劣る。
Figure JPOXMLDOC01-appb-T000018
 (A) Mineral oil is used as the lubricating base oil, and the lubricating oil composition used for cooling the electric motor and lubricating the gears in the electric vehicle contains (C) an ethylene-α-olefin copolymer. Comparing Examples 1 to 3 with Comparative Example 1 containing PMA instead of (C) ethylene-α-olefin copolymer, the lubricating oil composition of the present invention does not cause viscosity reduction even after the shear test. Therefore, the mechanism of the electric vehicle can be continuously protected for a long period of time. On the other hand, the lubricating oil compositions of Comparative Examples 2 and 3 containing PAO or PIB instead of (C) the ethylene-α-olefin copolymer had a thermal diffusivity of less than 7.0 × 10 -2 . Therefore, sufficient motor cooling performance cannot be obtained. (C) The ethylene-α-olefin copolymer has a methylene chain as a main skeleton and has a smaller degree of freedom at the molecular ends than PAO and PIB, so heat generation due to molecular vibration is suppressed, and it was used in the lubricating oil composition. It is considered that excellent cooling or heat dissipation performance is exhibited in this case. In addition, since fluidity is poor at low temperatures, the fuel economy is remarkably inferior in low-temperature environments.

Claims (10)

  1. 　以下の（Ａ１）～（Ａ３）の特徴を有する（Ａ）鉱物油、および／または以下の（Ｂ１）～（Ｂ３）の特徴を有する（Ｂ）合成油からなる潤滑油基油と、以下の（Ｃ１）～（Ｃ５）の特徴を有する（Ｃ）エチレン－α－オレフィン共重合体とを含有し、１００℃における動粘度が４～１０ｍｍ2／ｓである、電動車両における電動モーターの冷却および歯車の潤滑のために用いられる潤滑油組成物。
    （Ａ１）１００℃における動粘度が２～６ｍｍ2／ｓであること
    （Ａ２）粘度指数が１０５以上であること
    （Ａ３）流動点が－５℃以下であること
    （Ｂ１）１００℃における動粘度が１～９ｍｍ2／ｓであること
    （Ｂ２）粘度指数が１１０以上であること
    （Ｂ３）流動点が－３０℃以下であること
    （Ｃ１）エチレンモル含有率が３０～７０ｍｏｌ％の範囲にあること
    （Ｃ２）１００℃における動粘度が１０～５，０００ｍｍ2／ｓであること
    （Ｃ３）ハーゼン色度が３０以下であること
    （Ｃ４）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、ポリスチレン換算により得られた分子量において、分子量分布（Ｍｗ／Ｍｎ）が２．５以下であること
    （Ｃ５）下記式［１］
    Figure JPOXMLDOC01-appb-M000001
     （式中、ＰEはエチレン成分の含有モル分率を示し、ＰOはα－オレフィン成分の含有モル分率を示し、ＰOEは全ｄｙａｄ連鎖のエチレン－α－オレフィン連鎖のモル分率を示す。）
    で表されるＢ値が、１．１以上であること     Lubricating base oil made of (A) mineral oil having the following characteristics (A1) to (A3) and / or (B) synthetic oil having the following characteristics (B1) to (B3), (C) an ethylene-α-olefin copolymer having the characteristics of (C1) to (C5) and having a kinematic viscosity at 100°C of 4 to 10 mm 2 /s, for cooling an electric motor in an electric vehicle and A lubricating oil composition used for gear lubrication.
    (A1) Kinematic viscosity at 100°C is 2 to 6 mm 2 /s (A2) Viscosity index is 105 or more (A3) Pour point is -5°C or less (B1) Kinematic viscosity at 100°C ( B2 ) Viscosity index is 110 or more (B3) Pour point is -30°C or less (C1) Ethylene molar content is in the range of 30 to 70 mol% (C2) Kinematic viscosity at 100° C. of 10 to 5,000 mm 2 /s (C3) Hazen chromaticity of 30 or less (C4) Measured by gel permeation chromatography (GPC) and converted to polystyrene In the obtained molecular weight, the molecular weight distribution (Mw / Mn) is 2.5 or less (C5) the following formula [1]
    Figure JPOXMLDOC01-appb-M000001
     (In the formula, P E indicates the molar fraction of the ethylene component, PO indicates the molar fraction of the α-olefin component, and P OE indicates the molar fraction of the ethylene-α-olefin chain of all the dyad chains. show.)
    The B value represented by is 1.1 or more
  2. 　前記（Ｃ）エチレン－α－オレフィン共重合体が以下の（Ｃ６）～（Ｃ８）のいずれか１つ以上の特徴を有する請求項１に記載の潤滑油組成物。
    （Ｃ６）５０℃における熱拡散率が８．０×１０＾－５～１．０×１０＾－４ｍ＾２／ｓであること
    （Ｃ７）５０℃、２５０Ｖにおける体積抵抗率が１．０×１０＾１５～１．０×１０＾１７Ω・ｃｍであること
    （Ｃ８）５０℃における比誘電率が２．００～２．３０であること     The lubricating oil composition according to claim 1, wherein (C) the ethylene-α-olefin copolymer has one or more of the following characteristics (C6) to (C8).
    (C6) Thermal diffusivity at 50° C. is 8.0×10^-5 to 1.0×10^-4 m^2/s (C7) Volume resistivity at 50° C. and 250 V is 1.0× 10̂15 to 1.0×10̂17Ω·cm (C8) Relative permittivity at 50°C is 2.00 to 2.30
  3. 　前記（Ｃ）エチレン－α－オレフィン共重合体のエチレンモル含有率が４０～６０ｍｏｌ％の範囲にある請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the ethylene molar content of (C) the ethylene-α-olefin copolymer is in the range of 40 to 60 mol%.
  4. 　前記（Ｃ）エチレン－α－オレフィン共重合体の１００℃における動粘度が２０～２，５００ｍｍ2／ｓである請求項１に記載の潤滑油組成物。 2. The lubricating oil composition according to claim 1, wherein the (C) ethylene-α-olefin copolymer has a kinematic viscosity at 100° C. of 20 to 2,500 mm 2 /s.
  5. 　前記（Ｃ）エチレン－α－オレフィン共重合体のα－オレフィンがプロピレンである請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the α-olefin of the (C) ethylene-α-olefin copolymer is propylene.
  6. 　前記潤滑油基油と前記（Ｃ）エチレン－α－オレフィン共重合体との合計量を１００質量％とした場合の前記（Ｃ）エチレン－α－オレフィン共重合体の含有量が１～１０質量％である請求項１に記載の潤滑油組成物。 The content of the (C) ethylene-α-olefin copolymer when the total amount of the lubricating base oil and the (C) ethylene-α-olefin copolymer is 100% by mass is 1 to 10 mass %.
  7. 　前記電動車両が電気自動車、プラグインハイブリッド車、ハイブリッド車、または燃料電池車のいずれかである請求項１～６のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 6, wherein the electric vehicle is an electric vehicle, a plug-in hybrid vehicle, a hybrid vehicle, or a fuel cell vehicle.
  8. 　前記電動車両に装備された電気モーターがインホイールモーターである請求項１～６のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 6, wherein the electric motor installed in the electric vehicle is an in-wheel motor.
  9. 　前記電動車両が電動車いす、または電動カートのいずれかである請求項１～６のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 6, wherein the electric vehicle is either an electric wheelchair or an electric cart.
  10. 　前記電動車両が電動スケートボード、または電動ローラースケートのいずれかである請求項１～６のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 6, wherein the electric vehicle is either an electric skateboard or an electric roller skate.
PCT/JP2023/007952 2022-03-03 2023-03-03 Lubricant composition WO2023167307A1 (en)

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JP2006325369A (en) * 2005-05-20 2006-11-30 Nissan Motor Co Ltd Cooling apparatus of electric motor
JP2012031359A (en) * 2009-12-28 2012-02-16 Idemitsu Kosan Co Ltd Base oil for cooling of device, device-cooling oil containing the base oil, device to be cooled by the cooling oil, and device cooling method using the cooling oil
JP2013126280A (en) * 2011-12-14 2013-06-24 Nissan Motor Co Ltd Rotary electric machine
JP2016069405A (en) * 2014-09-26 2016-05-09 三井化学株式会社 Lubricant composition
JP2016108406A (en) * 2014-12-04 2016-06-20 東燃ゼネラル石油株式会社 Lubricating oil composition
JP2019154115A (en) * 2018-03-01 2019-09-12 本田技研工業株式会社 Cooling system for rotary electric machine, and rotary electric machine with the same
JP2021500463A (en) * 2017-10-20 2021-01-07 トタル マーケティング セルヴィス Composition for cooling and lubricating the vehicle drive system
JP2021164298A (en) * 2020-03-31 2021-10-11 日本電産株式会社 Driving device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006325369A (en) * 2005-05-20 2006-11-30 Nissan Motor Co Ltd Cooling apparatus of electric motor
JP2012031359A (en) * 2009-12-28 2012-02-16 Idemitsu Kosan Co Ltd Base oil for cooling of device, device-cooling oil containing the base oil, device to be cooled by the cooling oil, and device cooling method using the cooling oil
JP2013126280A (en) * 2011-12-14 2013-06-24 Nissan Motor Co Ltd Rotary electric machine
JP2016069405A (en) * 2014-09-26 2016-05-09 三井化学株式会社 Lubricant composition
JP2016108406A (en) * 2014-12-04 2016-06-20 東燃ゼネラル石油株式会社 Lubricating oil composition
JP2021500463A (en) * 2017-10-20 2021-01-07 トタル マーケティング セルヴィス Composition for cooling and lubricating the vehicle drive system
JP2019154115A (en) * 2018-03-01 2019-09-12 本田技研工業株式会社 Cooling system for rotary electric machine, and rotary electric machine with the same
JP2021164298A (en) * 2020-03-31 2021-10-11 日本電産株式会社 Driving device

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