JP2018115228A - Lubricant composition for automobile transmissions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricant composition for automobile transmissions that has extremely good shear stability, and strikes a balance between temperature viscosity properties and oil film retention ability at high levels.SOLUTION: A lubricant composition for automobile transmissions contains a lubricant base oil containing mineral oil with a 100°C kinematic viscosity of 2-6 mm/s, a viscosity index of 105 or more, and a pour point of -10°C or less, and an ethylene-α-olefin copolymer with an ethylene content of 55-85 mol%, a 100°C kinematic viscosity of 200-3,000 mm/s, and a molecular weight distribution of 2.5 or less, and having the melting point in a range of -30°C to -60°C. The lubricant composition has a 100°C kinematic viscosity of 4.0-9.0 mm/s.SELECTED DRAWING: None

Description

  The present invention relates to a lubricating oil composition for automobile transmissions.

  Lubricants such as gear oils, transmission oils, hydraulic oils, greases, etc., in addition to performances such as protection of internal combustion engines and machine tools and heat dissipation, wear resistance, heat resistance, sludge resistance, lubricating oil consumption characteristics, fuel efficiency, etc. Various performances are required. Moreover, in recent years, each required performance has been increasingly sophisticated as the internal combustion engine and machine tool used have high performance, high output, and severe operating conditions. Recently, in particular, the use environment of lubricating oil has become harsher, but there is a tendency for longer life due to consideration of environmental issues. In addition to improved heat resistance and oxidation stability, internal combustion engines and machine tools Therefore, there is a demand for suppression of viscosity reduction due to shear stress from the above, that is, improvement of the shear stability of the lubricating oil. On the other hand, in order to improve the energy conversion efficiency of the engine or ensure good lubricity of the engine in a cryogenic environment, the oil film of the lubricating oil is retained at a high temperature, and the fluidity is retained at a low temperature. Temperature viscosity characteristics are regarded as important. As an index of the temperature-viscosity characteristics described here, the temperature-viscosity characteristics can be quantified by the viscosity index calculated by the method described in JIS K2283, and a higher viscosity index indicates a more excellent temperature-viscosity characteristic. Represent.

Therefore, there is a demand for a material that has excellent heat resistance, oxidation stability, shear stability, and good temperature-viscosity characteristics for the lubricating oil.
In particular, transmission oils used in automobiles have been required to have excellent temperature viscosity characteristics more than ever, and furthermore, high fluidity at extremely low temperatures such as −40 ° C., that is, excellent low temperature viscosity characteristics. These viscosity characteristics are directly related to the fuel efficiency performance of automobiles. However, since the Kyoto Protocol was adopted in 1997, this performance improvement requirement has recently been reduced by governments around the world in terms of carbon dioxide emission regulations and fuel efficiency regulations for passenger cars. Or because future goals were set.

  Based on this, in order to achieve the fuel efficiency target, each part of the engine in the automobile transmission has been downsized to improve fuel efficiency, and the amount of lubricating oil used has also decreased. For this reason, the load applied to the lubricating oil has been increasing, and further extension of the life of the lubricating oil has been demanded. In particular, depending on the vehicle transmission oil for ordinary automobiles, in recent years, there has been a demand for non-replacement of the transmission oil itself. Therefore, further extension of the life of the lubricating oil is an urgent issue.

  Examples of transmissions for automobiles include manual transmissions, automatic transmissions, continuously variable transmissions, dual clutch transmissions, etc. In any transmission, transmission oil is subjected to shear stress from gears or metal belts. For this reason, the viscosity of the lubricating oil decreases as the base material molecules used in the lubricating oil are cleaved over the course of use. When the lubricating oil viscosity decreases, contact between gears and metal occurs, and the gears are significantly damaged. For this reason, it is necessary to prepare for the ideal lubrication of the used / deteriorated lubricating oil by predicting a decrease in viscosity during the period of use and increasing the initial viscosity at the time of manufacturing the lubricating oil. Naturally, if the base material used in the lubricating oil is excellent in shear stability, that is, if the life is long, it is not necessary to increase the initial viscosity, and as a result, the agitation resistance of the lubricating oil to the gear can be lowered, so that the fuel efficiency can be improved. Can be planned.

  Furthermore, as a measure to improve fuel efficiency in recent years, the viscosity of transmission oil has been lowered compared to the conventional system to reduce the agitation resistance due to lubricating oil, and the increase in initial viscosity in preparation for viscosity reduction is contrary to this measure. In addition, since the risk of metal contact in the gear is increasing due to the lower viscosity, there is a demand for a material with extremely high shear stability that does not cause a decrease in viscosity.

  The automotive gear oil defined by the Science of Automobile Engineers (SAE) remains within the same viscosity standard even after the shear test defined by CRC L-45-T-93 in J306, which is its viscosity standard. “Stay-in-grade” has been established, but in recent years there has been an increased risk of metal contact due to low viscosity in transmission oils, so that there is no lack of lubrication performance after transmission use / degradation. It has been required to define a minimum viscosity after a shear test.

  In addition, the high oil film retention performance of the base material used in transmission oil is also an important performance for the above-described low viscosity transmission oil. That is, if the oil film holding performance of the base material is high, the viscosity can be further reduced, in other words, the fuel saving performance can be improved.

  Furthermore, if the temperature-viscosity characteristics are excellent, that is, if the temperature dependence of the lubricating oil viscosity is low, an increase in viscosity can be suppressed even in a low temperature environment, and as a result, the gear resistance due to the lubricating oil is relatively low compared to the prior art. , Fuel efficiency can be improved.

  Conventionally, in order to improve the temperature-viscosity characteristics of lubricating oil as a measure for improving fuel efficiency, a methacrylate copolymer or a methacrylic acid ester copolymer as exemplified in Patent Documents 1 to 4 is used as a viscosity modifier or a viscosity index. Lubricating oil compositions used as improvers are known. Such copolymers are collectively referred to as polymethacrylates.

  Conventionally, it is known that the shear stability of a lubricating oil composition depends on the molecular weight of the components contained. That is, a lubricating oil composition containing a component having a higher molecular weight is likely to cause a viscosity drop due to shear stress, and this viscosity reduction rate correlates with the molecular weight of the contained component.

  On the other hand, the temperature viscosity property and the low temperature viscosity property of the lubricating oil composition are improved by containing more high molecular weight components. That is, the viscosity modifier or viscosity index improver used in the lubricating oil composition has a trade-off relationship in that although the temperature-viscosity characteristics improve as the molecular weight increases, the shear stability decreases. In this regard, there is room for improvement from the viewpoint of achieving both shear stability and temperature-viscosity characteristics.

  In recent years, poly-α-olefin (PAO) has been used as a synthetic lubricant base material for the purpose of improving shear stability. Such PAO can be obtained by oligomerizing a higher α-olefin with an acid catalyst, as described in Patent Documents 5 to 7 and the like.

  On the other hand, as described in Patent Document 8, an ethylene / α-olefin copolymer, like PAO, can be used as a synthetic lubricating oil having excellent viscosity index, oxidation stability, shear stability, and heat resistance. Are known.

  As a method for producing an ethylene / α-olefin copolymer used as a synthetic lubricating oil, a method using a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound as described in Patent Document 9 and Patent Document 10 has been conventionally used. Has been used. As such an ethylene / α-olefin copolymer, an ethylene / propylene copolymer is mainly used.

  Further, as a method for producing a copolymer with high polymerization activity, there is a method using a catalyst system comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) as described in Patent Document 11 and Patent Document 12. Patent Document 13 discloses a method for producing a synthetic lubricating oil comprising an ethylene / α-olefin copolymer obtained by using a catalyst system in which a specific metallocene catalyst and an aluminoxane are combined.

  In recent years, the demand for PAO or ethylene / propylene copolymer, which is a synthetic lubricant base material excellent in viscosity temperature characteristics and shear stability, has been increasing, but there is room for improvement in viscosity index from the viewpoint of further fuel saving. There is.

Based on this requirement, a PAO obtained by a method using a catalyst system composed of a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) as described in Patent Documents 14 to 17 has been invented.
However, PAO obtained with a metallocene catalyst has a trade-off relationship in that, when used in a lubricating oil, the temperature-viscosity characteristics are improved as the molecular weight is increased, but the shear stability is lowered. About this point, it has not reached sufficient solution from a viewpoint of coexistence of shear stability and temperature viscosity property.

In particular, the dual clutch transmission oil using a wet clutch has a gear mechanism similar to that of a manual transmission oil, so that a high shear stress is applied to the transmission oil. On the other hand, since it is a wet clutch, the filling amount is much higher than that of the manual transmission. Since the influence of agitation resistance due to transmission oil increases and the influence of transmission oil increases, it is required to achieve both extremely high shear stability and temperature-viscosity characteristics.
On the other hand, Patent Documents 18 to 19 propose lubricating oil compositions containing a specific ethylene-α-olefin copolymer.

JP-A-8-53683 Japanese Patent No. 4414123 Japanese Patent No. 3816847 JP 2009-256665 A U.S. Pat. No. 3,780,128 U.S. Pat. No. 4,032,591 JP-A-1-163136 JP-A-57-117595 Japanese Patent Publication No.2-1163 Japanese Patent Publication No.2-7998 JP 61-221207 A Japanese Patent Publication No. 7-121969 Japanese Patent No. 2796376 JP 2001-335607 A JP-T-2004-506758 Special table 2009-503147 Special table 2009-514991 gazette Japanese Patent Laid-Open No. 2006-69404 Japanese Patent Laid-Open No. 2006-69405

  The problem to be solved by the present invention in view of such problems in the prior art is that the shear stability is extremely excellent and includes the same lubricating base oil from the viewpoint of fuel efficiency and energy saving of automobiles. It is an object of the present invention to provide a lubricating oil composition for an automobile transmission that has a high level of temperature viscosity characteristics, low temperature viscosity characteristics, and oil film retention performance in a well-balanced manner as compared with other lubricating oils.

  As a result of intensive studies to develop a lubricating oil composition for automobile transmissions having extremely excellent performance, the present inventors have found that a specific ethylene-α-olefin (co) heavy is used for a specific lubricating base oil. It has been found that a lubricating oil composition containing a coalescence and satisfying specific conditions can solve the above-mentioned problems, and has completed the present invention. Specifically, the present invention includes the following aspects.

[1] A lubricating base oil containing a mineral oil (A) having the following characteristics (A1) to (A3), and an ethylene-α-olefin copolymer having the following characteristics (B1) to (B5) A lubricating oil composition for automobile transmissions containing (B) and having a kinematic viscosity at 100 ° C. of 4.0 to 9.0 mm ² / s.
(A1) Kinematic viscosity at 100 ° C. is 2.0 to 6.5 mm ² / s (A2) Viscosity index is 110 or more (A3) Pour point is −20 ° C. or less (B1) Ethylene (B2) Kinematic viscosity at 100 ° C. is 200 to 3,000 mm ² / s (B3) 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 (B4) The pour point is 0 ° C. or less (B5) from −30 ° C. in the differential scanning calorimetry (DSC) measurement. It has a melting point with a peak in the range of −60 ° C. and a heat of fusion (ΔH) of 25 J / g or less. [2] Ethylene of the ethylene-α-olefin copolymer (B) The lubricating oil composition for automobile transmissions according to [1], wherein the content is in the range of 58 to 70 mol%.
[3] The lubricating oil composition for an automobile transmission according to [1] or [2], wherein the ethylene-α-olefin copolymer (B) has a kinematic viscosity at 100 ° C. of 500 to 2,500 mm ² / s. .
[4] The lubricating oil composition for automobile transmissions according to any one of [1] to [3], wherein the α-olefin of the ethylene-α-olefin copolymer (B) is propylene.

  The lubricating oil composition for an automotive transmission according to the present invention is a lubricating oil composition that is superior in balance with high levels of shear stability, temperature-viscosity characteristics, and low-temperature viscosity characteristics compared to conventional lubricating oils containing the same lubricating base oil. It can be suitably applied to a transmission for an automobile, and is suitable as a manual transmission oil for an automobile, an automatic transmission oil for an automobile, a dual clutch transmission oil for an automobile, and the like.

Hereinafter, the automotive lubricating oil composition according to the present invention (hereinafter also simply referred to as “lubricating oil composition”) will be described in detail.
The automotive lubricating oil composition according to the present invention contains a lubricating base oil and an ethylene-α-olefin copolymer (B), and has a kinematic viscosity at 100 ° C. of 4.0 to 9.0 mm ² / s. And the lubricating base oil contains mineral oil (A).

<Lubricant base oil>
The lubricating base oil used in the present invention differs in performance and quality such as viscosity characteristics, heat resistance, and oxidation stability depending on its production method and purification method. API (American Petroleum Institute) classifies lubricant 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, as shown in Table 1.

<(A) Mineral oil>
The mineral oil (A) has the following features (A1) to (A3).
(A1) The kinematic viscosity at 100 ° C. is ² to 6 mm ² / s. The value of this kinematic viscosity is measured according to the method described in JIS K2283. The kinematic viscosity at 100 ° C. of the mineral oil (A) is 2.0 to 6.5 mm ² / s, preferably 2.5 to 5.8 mm ² / s, more preferably 2.8 to 4.5 mm ² / s. It is. When the kinematic viscosity at 100 ° C. is in this range, the lubricating oil composition of the present invention is excellent in terms of volatility and temperature viscosity characteristics.

(A2) Viscosity index is 110 or more The value of this viscosity index is measured according to the method described in JIS K2283. The viscosity index of the mineral oil (A) is 110 or more, preferably 115 or more. When the viscosity index is within this range, the lubricating oil composition of the present invention has excellent temperature viscosity characteristics.

(A3) The pour point is −20 ° C. or less. The value of the pour point is measured according to the method described in ASTM D97. The pour point of the mineral oil (A) is −20 ° C. or lower, preferably −25 ° C. or lower. When the pour point is in this range, the lubricating oil composition of the present invention has excellent low-temperature viscosity characteristics when the mineral oil (A) is used in combination with a pour point depressant.

The mineral oil (A) in the present invention belongs to groups I to III in the above-mentioned API category.
The quality of the mineral oil is as described above, and the above-described mineral oils of the respective qualities are obtained by the refining method. Specifically, as the mineral oil (A), a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking. Examples thereof include those refined by one or more treatments such as solvent dewaxing and hydrorefining, or lubricating base oils such as wax isomerized mineral oil.

  In particular, 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 are sometimes treated as Group III + lubricating base oils, for example, patent documents EP0776959, EP0668342, WO97 / 21788, WO00 / 15736, WO00 / 14188, WO00 / 14187, WO00 / 14183. , WO 00/14179, WO 00/08115, WO 99/41332, EP 1029029, WO 01/18156 and WO 01/57166.

  In the lubricating oil composition of the present invention, the mineral oil (A) may be used alone as the lubricating base oil, or an arbitrary mixture of two or more kinds of lubricating oils selected from the mineral oil (A). Etc. may be used, or may be used in combination with a synthetic oil described later.

<Ethylene-α-olefin copolymer (B)>
The ethylene-α-olefin copolymer (B) according to the present invention has the following characteristics (B1) to (B5).

(B1) The ethylene content is 55 to 85 mol%. The ethylene content of the ethylene-α-olefin copolymer (B) is 55 to 85 mol%, preferably 58 to 70 mol%, particularly preferably 60. -68 mol%. If it is too low, the viscosity temperature characteristics of the resulting lubricating oil composition will deteriorate, and if it is too high, the ethylene chain in the molecule will extend, resulting in high crystallinity of the ethylene-α-olefin copolymer. When expressed, the low-temperature viscosity characteristics of the resulting lubricating oil composition may be deteriorated.

The ethylene content of the ethylene-α-olefin copolymer (B) is measured by ¹³ C-NMR according to the method described in “Polymer Analysis Handbook” (published by Asakura Shoten, P163-170). Moreover, it is also possible to measure using the Fourier transform infrared spectroscopy (FT-IR) by making the sample calculated | required by this method into a known sample.

(B2) The kinematic viscosity at 100 ° C. is 200 to 3,000 mm ² / s. This kinematic viscosity value is measured by the method described in JIS K2283. The kinematic viscosity at 100 ° C. of the ethylene-α-olefin copolymer (B) is 200 to 3,000 mm ² / s, preferably 500 to 2,500 mm ² / s, more preferably 540 to 2,200 mm ² / s. It is. It is preferable that the kinematic viscosity at 100 ° C. of the ethylene-α-olefin copolymer (B) is within the above range in terms of shear stability and low temperature viscosity characteristics of the lubricating oil composition.

(B3) Molecular weight distribution is 2.5 or less The molecular weight distribution of the ethylene-α-olefin copolymer (B) according to the present invention is measured by gel permeation chromatography (GPC) according to the method described later, and is standard. It is calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by polystyrene conversion. This Mw / Mn is 2.5 or less, preferably 2.3 or less, more preferably 2.0 or less. When the molecular weight distribution exceeds this range, the viscosity of the lubricating oil composition changes due to the volatilization of low molecular weight components or the shear stability of the lubricating oil composition deteriorates when used in a high temperature environment. The molecular weight distribution of the ethylene-α-olefin copolymer (B) is preferably at least 1.6. When the molecular weight distribution is in this range, the viscosity temperature characteristic of the lubricating oil composition is excellent.

(B4) The pour point is 0 ° C. or less. The value of the pour point is measured according to the method described in ASTM D97. The pour point of the ethylene-α-olefin copolymer (B) is 0 ° C. or lower, preferably −3 ° C. or lower, more preferably −5 ° C. or lower. When the pour point is within this range, the lubricating oil composition of the present invention has excellent low temperature viscosity characteristics.

(B5) It has a melting point with a peak in the range of −30 ° C. to −60 ° C. and a heat of fusion (ΔH) of 25 J / g or less as measured by differential scanning calorimetry (DSC). The melting point (Tm) and heat of fusion (ΔH) of the union (B) were measured by differential scanning calorimetry (DSC), heated to 150 ° C., cooled to −100 ° C., and then heated at a rate of 10 ° C. / When the temperature is raised to 150 ° C. in minutes, the DSC curve is obtained with reference to JIS K7121. The ethylene-α-olefin copolymer (B) has a differential scanning calorimetry (DSC) condition of −30 ° C. to −60 ° C., preferably −35 ° C. to −58 ° C., more preferably −40 ° C. A melting point peak is observed in the range of from ℃ to -50 ℃. The heat of fusion (ΔH) (unit: J / g) measured from the peak of the melting point (Tm) observed at this time is 25 J / g or less, preferably 23 J / g or less, more preferably 20 J / g or less. When the melting point peak and the heat of fusion are in this range, it has excellent low temperature viscosity characteristics without solidifying in a temperature range of −40 ° C. or higher, and the ethylene-α-olefin copolymer (B) has an intramolecular structure, A lubricating oil composition having excellent temperature-viscosity characteristics can be obtained by intermolecular interaction.

  Examples of the α-olefin used in the ethylene-α-olefin copolymer (B) according to the present invention include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl- 3 to 20 carbon atoms such as 1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and vinylcyclohexane A linear or 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, and the resulting copolymer was used. Propylene is most preferred from the viewpoint of the shear stability of the lubricating oil composition. These α-olefins can be used alone or in combination of two or more.

  In addition, the polymerization can also proceed by coexisting at least one other monomer selected from a polar group-containing monomer, an aromatic vinyl compound, and a cyclic olefin in the reaction system. The other monomer can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less based on 100 parts by mass in total with ethylene and the α-olefin having 3 to 20 carbon atoms.

  Examples of the polar group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid and maleic anhydride, and metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, acrylic acid α, β-unsaturated carboxylic esters such as n-propyl, methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated glycidyl such as glycidyl acrylate and glycidyl methacrylate, etc. Can be illustrated.

  Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, Examples thereof include p-chlorostyrene, divinylbenzene, α-methylstyrene, and allylbenzene.

  Examples of the cyclic olefin 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 method for producing the ethylene-α-olefin copolymer (B) according to the present invention is not particularly limited, but vanadium compounds and organic compounds described in JP-B2-1163 and JP-B-2-7998 are used. Examples thereof include a method using a vanadium catalyst comprising an aluminum compound. Further, as a method for producing a copolymer with high polymerization activity, metallocene compounds such as zirconocene and organoaluminum as described in JP-A-61-221207, JP-B-7-121969, and Japanese Patent No. 2796376. A method using a catalyst system composed of an oxy compound (aluminoxane) may be used, and a metallocene catalyst is more preferably used from the viewpoint of the appearance of the resulting copolymer. In the method using a vanadium catalyst, the transparency of the production of the lubricating oil composition obtained by giving a copolymer that becomes cloudy as the ethylene content increases may be impaired as compared with the method using a metallocene catalyst.

  The ethylene-α-olefin copolymer (B) according to the present invention includes a crosslinked metallocene compound (a) represented by the following general formula [I], an organometallic compound (b-1), an organoaluminum oxy compound ( in the presence of an olefin polymerization catalyst comprising at least one compound (b) selected from the group consisting of b-2) and a compound (b-3) which reacts with the bridged metallocene compound (a) to form an ion pair. It can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.

<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 the formula [I] will be described below.
^{(Y, M, R 1 ~R} 14, Q, n and j)
Y is a group 14 atom, and examples thereof include a carbon atom, a silicon atom, a germanium atom, and a tin atom, preferably a carbon atom or a silicon atom, and more preferably a carbon atom.

M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom.
R ^{1 to} R ¹² are 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, or an atom or substituent selected from the group consisting of a halogen-containing group. These may be the same or different. Further, adjacent substituents from R ¹ to R ¹² may be bonded to each other to form a ring, or may not be bonded to each other.

  Here, as a C1-C20 hydrocarbon group, a C1-C20 alkyl group, a C3-C20 cyclic saturated hydrocarbon group, a C2-C20 chain unsaturated hydrocarbon group, Examples thereof include cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms, alkylene groups having 1 to 20 carbon atoms, and arylene groups having 6 to 20 carbon atoms.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, and n-hexyl which are linear saturated hydrocarbon groups. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, etc., branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group 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 Examples include 2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, and cyclopropylmethyl group. Preferably carbon number of an alkyl group is 1-6.

  Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, which are cyclic saturated hydrocarbon groups, 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, which is a group in which a hydrogen atom of a cyclic saturated hydrocarbon group such as 2-adamantyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms, 4 Examples include -cyclohexylcyclohexyl group and 4-phenylcyclohexyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5-11.

  Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group) and 1-methylethenyl group (isopropenyl group) which are alkenyl groups. Examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group (propargyl group) which are alkynyl groups. The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

  Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group, anthracenyl group and the like, which are cyclic unsaturated hydrocarbon groups 3-methylphenyl group (m-tolyl group) and 4-methylphenyl group (p-tolyl group), which are groups in which a 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 cyclic hydrocarbon group having 3 to 19 carbon atoms or a cyclic unsaturated hydrocarbon group, such as a mesityl group) or the like. Benzyl group is a group which is replaced by a hydrocarbon group, such as cumyl group and the like. The number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6-10.

  Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), an ethylmethylene group, a methylethylene group, and an n-propylene group. Preferably carbon number of an alkylene group is 1-6.

  Examples of the arylene group having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group, 4,4'-biphenylylene group and the like. The carbon number of the arylene group is preferably 6-12.

  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 groups in which a carbon atom is replaced with a silicon atom in a hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, t-butyldiphenylsilyl group, pentamethyldisiranyl group, and trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the nitrogen-containing group, or an amino group, in a hydrocarbon group or a silicon-containing group having 1 to 20 carbon atoms mentioned above, = CH- group where structural unit is replaced by a nitrogen atom, is -CH _2-structural units carbon atoms Dimethyl which is a group in which a hydrocarbon group having 1 to 20 hydrocarbons is replaced by a nitrogen atom bonded thereto, or a group in which a —CH ₃ structural unit is replaced by a nitrogen atom or a nitrile group to which a hydrocarbon group having 1 to 20 carbon atoms is bonded 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 preferable.

Examples of the oxygen-containing group include a hydroxyl group, a 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 by an oxygen atom or a carbonyl group, or — A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a 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 Examples include acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, and pyranyl group. The As the oxygen-containing group, a methoxy group is preferable.

Examples of halogen atoms include group 17 elements such as fluorine, chlorine, bromine and iodine.
Examples of the halogen-containing group include a trifluoromethyl group, tribromo, which is a group in which a hydrogen atom is substituted with a halogen atom in the above-described hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, nitrogen-containing group or oxygen-containing group. Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.

Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair.
Details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, a chlorine atom is preferable. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.

  Examples of the anionic ligand 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.

  Examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, and the like. An ether compound etc. can be illustrated.

j is an integer of 1 to 4, preferably 2.
n is an integer of 1 to 4, preferably 1 or 2, and 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. An atom or a substituent, which may be the same or different. R ¹³ and R ¹⁴ may be bonded to each other to form a ring, or may not be bonded to each other.

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 example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but is a phenyl group, 1-naphthyl group, 2-naphthyl which is a substituent derived from an aromatic compound. Groups, 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 are exemplified. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.

  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. .

  The substituted aryl group partially overlaps with the example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but one or more hydrogen atoms of the aryl group are hydrocarbon groups having 1 to 20 carbon atoms, Examples include groups substituted with at least one substituent selected from the group consisting of aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups. 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-morpholinyl group Nyl group, 4-methoxyphenyl group, 4-ethoxyphenyl 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.

  In the bridged metallocene compound (a) represented by the above formula [I], 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].

In the formula [II], Y, M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , Q and j are defined as described above.
The bridged metallocene compound (a-1) has a simplified production process and reduced production costs as compared with the compound in which n in the above formula [I] is an integer of 2 to 4, and this bridged metallocene compound (a- By using 1), the advantage that the production cost of the ethylene-α-olefin copolymer (B) is reduced can be obtained.

In the bridged metallocene compound (a-1) represented by the above formula [II], R ¹ , R ² , R ³ and R ⁴ are preferably all hydrogen. Such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-2)”) is represented by the following general formula [III].

In the formula [III], the definitions of Y, M, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , Q and j are as described above. It is as follows.
The bridged metallocene compound (a-2) is a production process compared to a compound in which any 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 by using this bridged metallocene compound (a-2), the production cost of the ethylene-α-olefin copolymer (B) is reduced. In general, it is known that the randomness of the ethylene-α-olefin copolymer (B) is reduced by performing high-temperature polymerization, but the olefin polymerization catalyst containing the crosslinked metallocene compound (a-2) When ethylene and one or more monomers selected from α-olefins having 3 to 20 carbon atoms are copolymerized in the presence, the resulting ethylene-α-olefin copolymer (B) even in high-temperature polymerization The advantage of high randomness is also obtained.

In the bridged metallocene compound (a-2) represented by the above formula [III], any one of R ¹³ and R ¹⁴ is preferably an aryl group or a substituted aryl group. Such a bridged metallocene compound (a-3) has an ethylene-α-olefin copolymer (B) produced as compared to the case where both R ¹³ and R ¹⁴ are substituents other than aryl groups and substituted aryl groups. An advantage is obtained that the amount of unsaturated bonds therein is small.

In the bridged metallocene compound (a-3), one of R ¹³ and R ^14, an aryl group or a substituted aryl group, more preferably the other is an alkyl group having 1 to 20 carbon atoms, R ¹³ and It is particularly preferred that any one of R ¹⁴ is an aryl group or a substituted aryl group, and the other is a methyl group. Such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-4)”) is produced in comparison with the case where both R ¹³ and R ¹⁴ are aryl groups or substituted aryl groups. Advantage of excellent balance between unsaturated bond amount in olefin copolymer (B) and polymerization activity, and reduction in production cost of ethylene-α-olefin copolymer (B) by using this crosslinked metallocene compound. Is obtained.

  In the case where the polymerization is carried out under certain conditions of the 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 as a polymerization monomer. Causes a problem of lowering the polymerization rate. Since the polymerization reactor has a limited total internal pressure that is allowed in its design, particularly when excessive hydrogen introduction is required when producing a low molecular weight olefin polymer, the olefin partial pressure is significantly reduced. Polymerization activity may decrease. However, in the case of producing the ethylene-α-olefin copolymer (B) in the present invention using the bridged metallocene compound (a-4), compared with the case where the bridged metallocene compound (a-3) is used, a polymerization reactor. The amount of hydrogen introduced into the catalyst is reduced, the polymerization activity is improved, and the production cost of the ethylene-α-olefin copolymer (B) is reduced.

In the bridged metallocene compound (a-4), R ⁶ and R ¹¹ may be bonded to adjacent substituents to form a ring, and the alkyl group having 1 to 20 carbon atoms and 1 to 20 carbon atoms An alkylene group is preferred. In such a bridged metallocene compound (hereinafter also referred to as “bridged metallocene compound (a-5)”), R ⁶ and R ¹¹ are substitutions other than alkyl groups having 1 to 20 carbon atoms and alkylene groups having 1 to 20 carbon atoms. Compared with a compound substituted with a group, the production process is simplified, the production cost is reduced, and by using this bridged metallocene compound (a-5), the production cost of the ethylene-α-olefin copolymer (B) The advantage that is reduced is obtained.

  Bridged metallocene compound (a) represented by the above general formula [I], bridged metallocene compound (a-1) represented by the above general formula [II], bridged metallocene compound represented by the above general formula [III] ( In a-2) and the 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 bridged metallocene compound in which M is a zirconium atom, M is a titanium atom or Compared with the case of a hafnium atom, the polymerization activity is high, and there are obtained advantages that the production cost of the ethylene-α-olefin copolymer (B) is reduced.

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-butylful) Oreniru)] zirconium dichloride, [cyclohexylidene (eta ⁵ - cyclopentadienyl) (eta ^5-3,6-di -t- butyl-fluorenyl)] zirconium dichloride, [cyclohexylidene (eta 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 -octamethyloctahydrodibenzo Fluorenyl)] zirconium dichloride, diphenylmethylene {η ^5- (2-methyl-4-i-propylcyclo) Pentadienyl)} (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-butylful) Oreniru)] zirconium dichloride, [methylphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^5-3,6-di -t- butyl-fluorenyl)] zirconium dichloride, [methylphenylmethylene (eta 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-butylfluorene) Nyl)] zirconium dichloride, [methyl (3-methylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyloctahydrodibenzofluorenyl)] zirconium dichloride, [methyl (3-methylphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ⁵ - tetramethyl octahydro-dibenzo fluorenyl)] zirconium Mujikurorido,
[Diphenylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -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-butylfluorene) Nyl)] zirconium dichloride, [bis (3-methylphenyl) silylene (η ⁵ -cyclopentadienyl) (η ⁵ -octamethyloctahydrodibenzofluorenyl)] zirconium dichloride, [bis (3-methylphenyl) silylene (eta ⁵ - cyclopentadienyl) (eta ⁵ - tetramethyl octahydro-dibenzo fluorenyl) zirconium dichloride De,
[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.

Although the compound which replaced the zirconium atom of these compounds with the hafnium atom, the compound which replaced the chloro ligand with the methyl group, etc. are illustrated, bridged metallocene compound (a) is not limited to these illustrations. In addition, 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 group is represented.

<Compound (b)>
The polymerization catalyst used in the present invention reacts with the above-mentioned bridged metallocene compound (a), organometallic compound (b-1), organoaluminum oxy compound (b-2), and bridged metallocene compound (a) to form ions. It contains at least one compound (b) selected from the group consisting of compound (b-3) forming a pair.

As the organometallic compound (b-1), specifically, organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the following periodic table are used.
(B-1a) formula _{^{R a m Al (OR b)}} n H p X q
(In the formula, R ^a and R ^b may be the same or different from each other and each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <m. ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3)
An organoaluminum compound represented by

Such compounds include tri-n-alkyl aluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisopropylaluminum, triisobutylaluminum, tri sec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-branched alkylaluminum such as tri-2-ethylhexylaluminum, tricyclohexylaluminum, tricyclooctylaluminum Tricycloalkylaluminum such as triphenylaluminum, triarylaluminum such as tri (4-methylphenyl) aluminum, di Isopropyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, z ≦ 2x.) Alkenyl aluminum such as isoprenyl aluminum, etc., alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, dialkyl such as dibutyl aluminum butoxide aluminum alkoxide, ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide, general formula ^{_{R a 2.5 Al (OR b)}} 0.5 etc. Alkoxy aluminum aryloxides such as partially alkoxylated alkylaluminum, diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide) having the average composition represented, dimethylaluminum chloride Dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, alkylaluminum sesquichloride such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum such as ethylaluminum dichloride Partially halogenated alkylaluminums such as dihalides, Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride, and other partially hydrogenated alkylaluminums, ethylaluminum ethoxychloride, butylaluminum butoxychloride And partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxybromide. A compound similar to the compound represented by the general formula R ^a _m Al (OR ^b ) _n H _p X _q can also be used. For example, organoaluminum in which two or more aluminum compounds are bonded via a nitrogen atom. A compound can be mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

(B-1b) 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 alkylated product of a Group 1 metal of the periodic table and aluminum.

Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
(B-1c) General formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). , M ³ is Mg, Zn or Cd.) Dialkyl compounds of Group 2 or Group 12 metals of the Periodic Table.

  As the organoaluminum oxy compound (b-2), a conventionally known aluminoxane can be used as it is. Specific examples include compounds represented by the following general formula [IV] and compounds represented by the following general formula [V].

In the formulas [IV] and [V], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.
In particular, methylaluminoxane wherein R is a methyl group and n is 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds.

  In the present invention, when copolymerization of ethylene and an α-olefin having 3 or more carbon atoms is carried out at a high temperature, a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 is also applied. be able to. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxane having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used. The “benzene-insoluble organoaluminum oxy compound” sometimes 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 in terms of Al atom. It is a compound that is 2% or less and is insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound (b-2) include modified methylaluminoxane represented by the following general formula [VI].

In formula [VI], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more.
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. Such MMAO can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584. In addition, those prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. and having R as an isobutyl group are commercially available under the names MMAO and TMAO. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, it is based on benzene among the compounds represented by the above formula [IV] and [V]. Unlike insoluble or hardly soluble compounds, it is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.

  Furthermore, the organoaluminum oxy compound (b-2) can also include an organoaluminum oxy compound containing boron represented by the following general formula [VII].

In the formula [VII], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
As the compound (b-3) (hereinafter sometimes abbreviated as “ionized ionic compound” or simply “ionic compound”) that forms an ion pair by reacting with the bridged metallocene compound (a), Japanese Patent Application Laid-Open No. Hei. 1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in publications. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VIII].

In the 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 as or different from each other, and are substituents selected from 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. Yes, preferably a substituted aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (4-methylphenyl) carbenium cation, and tris (3,5-dimethylphenyl) carbenium cation. .

  Specific examples of the ammonium cation include trialkyl-substituted ammonium such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dialkylanilinium cation such as cation, N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, diisopropylammonium cation, And dialkylammonium cations such as dicyclohexylammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (4-methylphenyl) phosphonium cation, and tris (3,5-dimethylphenyl) phosphonium cation.

R ^{e +} is preferably a carbenium cation or an ammonium cation among the above specific examples, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

  Of the ionized ionic compounds preferably used in the present invention, compounds containing a carbenium cation include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis {3, 5-di- (trifluoromethyl) phenyl} borate, tris (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate, etc. It can be illustrated.

  Among the ionized ionic compounds preferably used in the present invention, compounds containing a trialkyl-substituted ammonium cation 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-dimethylpheny ) 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, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (4-methylphenyl) borate Dioctadecylmethylammonium tetrakis (4-methylphenyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetra (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis {4- (trifluoromethyl) phenyl} borate, dioctadecylmethylammonium tetrakis {3 , 5-di (trifluoromethyl) phenyl} borate, dioctadecylmethylammonium and the like.

  Among the ionized ionic compounds preferably used in the present invention, N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) are compounds containing N, N-dialkylanilinium cations. ) 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 And the like can be exemplified tetrakis (pentafluorophenyl) borate.

  Among the ionized ionic compounds preferably used in the present invention, examples of the compound containing a dialkylammonium cation include di-n-propylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds exemplified by JP-A-2004-51676 can also be used without limitation.
Said ionic compound (b-3) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  As the organometallic compound (b-1), trimethylaluminum, triethylaluminum and triisobutylaluminum that are easily available for commercial products are preferable. Of these, triisobutylaluminum that is easy to handle is particularly preferred.

  As the organoaluminum oxy compound (b-2), methylaluminoxane which is easily available for commercial products and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferable. Of these, MMAO having improved solubility in various solvents and storage stability is particularly preferable.

  As the ionic compound (b-3), triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylaniline are easily obtained as a commercial product and greatly contribute to the improvement of polymerization activity. Nium tetrakis (pentafluorophenyl) borate is preferred.

  As the compound (b), since the polymerization activity is greatly improved, a combination of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate, and triisobutylaluminum and N, N-dimethylanilinium tetrakis (penta A combination with (fluorophenyl) borate is particularly preferred.

<Carrier (c)>
In this invention, you may use a support | carrier (c) as a structural component of an olefin polymerization catalyst as needed.

  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, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, THO ₂ or the like, or a composite or mixture containing these, for example, using natural or synthetic zeolites, SiO ₂ -MgO, etc. _{SiO 2 -Al 2 O 3, SiO} 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO can do. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred. Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 0.5 to 300 μm, preferably 1.0 to 200 μm, and has a specific surface area. Is in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Alternatively, an inorganic chloride dissolved in a solvent such as alcohol and then precipitated in a fine particle form by a precipitating agent may be used.

Clay is usually composed mainly of clay minerals. In addition, the ion-exchangeable layered compound is a compound having a crystal structure in which the surfaces to be formed are stacked in parallel with a weak binding force by ionic bonds or the like, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite, 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 (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O. The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Further, the introduction of another substance (guest compound) between the layered compounds in this way 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) Group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ^+. . These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, hydrolytic polycondensation of metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) The obtained polymer, a colloidal inorganic compound such as SiO _2, etc. can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

Of these, 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 fine particle solids having a particle size in the range of 0.5 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

  High-temperature polymerization is possible by a polymerization method using an olefin polymerization catalyst capable of producing a highly random ethylene-α-olefin copolymer (B). That is, by using the olefin polymerization catalyst, it is possible to suppress a decrease in randomness of the ethylene-α-olefin copolymer (B) generated during high temperature polymerization. In the solution polymerization, the viscosity of the polymerization solution containing the produced ethylene-α-olefin copolymer (B) decreases at a high temperature, so that the ethylene-α-olefin copolymer (B ) Can be increased, and as a result, productivity per polymerization vessel is improved. The copolymerization of ethylene and α-olefin in the present invention can be carried out in any of liquid phase polymerization methods such as solution polymerization and suspension polymerization (slurry polymerization) or gas phase polymerization methods. Solution polymerization is particularly preferable from the viewpoint of obtaining the maximum amount of water.

The usage and order of addition of each component of the olefin polymerization catalyst is arbitrarily selected. Moreover, at least 2 or more of each component in a catalyst may be contacted previously.
The bridged metallocene compound (a) (hereinafter also referred to as “component (a)”) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol per liter of reaction volume. Used in quantity.

  The organometallic compound (b-1) (hereinafter also referred to as “component (b-1)”) is a molar ratio of the component (b-1) to the transition metal atom (M) in the component (a) [( b-1) / M] is usually used in an amount of 0.01 to 50,000, preferably 0.05 to 10,000.

  The organoaluminum oxy compound (b-2) (hereinafter also referred to as “component (b-2)”) includes an aluminum atom in component (b-2) and a transition metal atom (M) in component (a). The molar ratio [(b-2) / M] 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 of the component (b-3) to the transition metal atom (M) in the component (a) [( b-3) / M] is usually used in an amount of 1 to 10,000, preferably 1 to 5,000.

  The polymerization temperature is usually −50 ° C. to 300 ° C., preferably 30 to 250 ° C., more preferably 100 ° C. to 250 ° C., and further preferably 130 ° C. to 200 ° C. In the polymerization temperature range of the above range, as the temperature increases, the solution viscosity at the time of polymerization decreases, and the heat of polymerization is easily removed. 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 possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.
The molecular weight of the copolymer obtained can be adjusted by changing the hydrogen concentration or polymerization temperature in the polymerization system. Furthermore, it can also adjust with the quantity of the component (b) to be used. When hydrogen is added, the amount is suitably about 0.001 to 5,000 NL per 1 kg of the produced copolymer.

  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. Particularly preferred are hexane, heptane, octane, decane, and cyclohexane. The α-olefin itself that is the object of polymerization 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. However, from the viewpoint of reducing environmental impact and human health. From the viewpoint of minimizing the influence of the above, their use is not preferable.

  The kinematic viscosity at 100 ° C. of the ethylene-α-olefin copolymer (B) according to the present invention depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity is high, and if the molecular weight is low, the viscosity is low. Therefore, the kinematic viscosity at 100 ° C. is adjusted by adjusting the molecular weight. Moreover, the molecular weight distribution (Mw / Mn) of the polymer obtained can be adjusted by removing the low molecular weight component of the polymer obtained by a conventionally known method such as vacuum distillation. Further, the obtained polymer may be hydrogenated (hereinafter also referred to as hydrogenation) by a conventionally known method. If the unsaturated bond of the polymer obtained by hydrogenation is reduced, oxidation stability and heat resistance are improved.

The obtained ethylene-α-olefin copolymer (B) may be used alone, or two or more types having different molecular weights or different monomer compositions may be combined.
Moreover, the ethylene-α-olefin copolymer (B) may be graft-modified with functional groups, and these may be further secondary-modified. Examples of secondary modification include the method described in JP-T-2008-508402 and the like, such as the method described in JP-A-61-126120 and Japanese Patent No. 2593264.

<Lubricating oil composition for automobile transmission>
The lubricating oil composition for automobile transmissions according to the present invention contains a lubricating base oil composed of the mineral oil (A) and the ethylene-α-olefin copolymer (B).

The lubricating oil composition for automobile transmissions according to the present invention has a kinematic viscosity at 100 ° C. of 4.0 to 9.0 mm ² / s. This value of kinematic viscosity is the value measured by the method described in JIS K2283. If the kinematic viscosity at 100 ° C. of the lubricating oil composition for automobile transmissions exceeds 9.0 mm ² / s, the oil film holding performance of the lubricating oil itself is improved, so that the effect obtained by the present invention is not sufficiently exhibited. In addition, fuel efficiency is inferior. If the kinematic viscosity at 100 ° C. is excessively smaller than 4.0 mm ² / s, the oil film holding performance is insufficient, and the possibility of metal contact between the gears increases. The kinematic viscosity at 100 ° C. is preferably 4.0 to 9.0 mm ² / s, and more preferably 4.2 to 6.5 mm ² / s. Within this range, high fuel saving performance and extremely excellent shear stability can be obtained.

In the lubricating oil composition for an automobile transmission of the present invention, the blending ratio of the lubricating base oil composed of the mineral oil (A) and the ethylene-α-olefin copolymer (B) is a requirement in the intended use. Although not particularly limited as long as the characteristics are satisfied, the mass ratio of the lubricating base oil to the ethylene-α-olefin copolymer (B) (mass of lubricating base oil / copolymer (B )) Is 99/1 to 50/50, preferably 85/15 to 60/40, more preferably 80/20 to 65/35.
The lubricating oil composition for automobile transmissions of the present invention may contain the following synthetic oil.

<Synthetic oil>
Synthetic oils in the present invention is attributed to the group IV, or group V, in the above-described API categories, substantially 100 ° C. kinematic viscosity of 2mm ² / s~10mm ² / s.

Poly-α-olefins belonging to Group IV are acid catalysts as described in U.S. Pat. No. 3,780,128, U.S. Pat. No. 4,032,591, and JP-A-1-163136. Can be obtained by oligomerizing a higher α-olefin. Among these, as the poly-α-olefin, a low molecular weight oligomer of at least one olefin selected from olefins having 8 or more carbon atoms can be used. Poly -α- olefins, industrially also available, are commercially available in a 100 ° C. kinematic viscosity 2mm ² / s~10mm ² / s. For example, NEXBASE2000 series manufactured by NESTE, Spectrayn manufactured by ExxonMobil Chemical, Durasyn manufactured by Ineos Olymmers, Synfluid manufactured by Chevron Phillips Chemical, and the like can be mentioned.

  Examples of the synthetic oil belonging to Group V include alkylbenzenes, alkylnaphthalenes, isobutene oligomers or hydrides thereof, paraffins, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, esters, and the like.

  Most of alkylbenzenes and alkylnaphthalenes are usually dialkylbenzene or dialkylnaphthalene having an alkyl chain length of 6 to 14 carbon atoms. Such alkylbenzenes or alkylnaphthalenes are free of benzene or naphthalene and olefin. Manufactured by a Dell Kraft alkylation reaction. The alkylated olefin used in the production of alkylbenzenes or alkylnaphthalenes may be a linear or branched olefin or a combination thereof. These production 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 the ethylene-α-olefin copolymer (B).
The fatty acid ester is not particularly limited, and examples thereof include the following fatty acid esters consisting only of carbon, oxygen, and hydrogen. For example, a monoester produced from a monobasic acid and an alcohol; from a dibasic acid and an alcohol, Or diesters made from diols and monobasic acids or acid mixtures; diols, triols (eg trimethylolpropane), tetraols (eg pentaerythritol), hexaols (eg dipentaerythritol) and the like and monobasic acids or acid mixtures And 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. .

  From the viewpoint of compatibility with the ethylene-α-olefin copolymer (B) according to the present invention, the alcohol moiety constituting the ester is preferably an alcohol having a bifunctional or higher hydroxyl group, and the fatty acid moiety has a carbon number. Eight or more fatty acids are preferred. However, fatty acids having a carbon number of 20 or less, which are industrially easily available, are superior in terms of production cost. The fatty acid constituting the ester may be one kind, and even when a fatty acid ester produced using two or more kinds of acid mixtures is used, the effects of the present invention are sufficiently exhibited. More specifically, examples of the fatty acid ester include trimethylolpropane lauric acid stearic acid mixed triester and diisodecyl adipate, and these include saturated hydrocarbon components such as ethylene-α-olefin copolymer (B) and From the viewpoint of compatibility with stabilizers such as an antioxidant having a polar group, a corrosion inhibitor, an antiwear agent, a friction modifier, a pour point depressant, a rust inhibitor and an antifoaming agent which will be described later.

  Further, the lubricating oil composition for automobile transmissions of the present invention comprises an extreme pressure agent, a cleaning dispersant, a viscosity index improver, an antioxidant, a corrosion inhibitor, an antiwear agent, a friction modifier, a pour point depressant, Additives such as rusting agents and antifoaming agents may be included.

The following can be illustrated as an additive used for the lubricating oil composition of this invention, These can be used individually by 1 type or in combination of 2 or more types.
Extreme pressure agent is a generic term for those having an effect of preventing seizure when an automobile transmission is exposed to a high load state, and is not particularly limited, but is not limited to sulfides, sulfoxides, sulfones, thiophosphinates, thiols. Sulfur based extreme pressure agents such as carbonates, sulfurized fats and oils, sulfurized olefins; Phosphoric acids such as phosphate esters, phosphites, phosphate ester amine salts and phosphite amines; Halogens such as chlorinated hydrocarbons A compound etc. can be illustrated. Two or more of these compounds may be used in combination.

  By the time the extreme pressure lubrication conditions are reached, hydrocarbons or other organic components constituting the lubricating oil composition are carbonized before the extreme pressure lubrication conditions by heating and shearing, and a carbide film is formed on the metal surface. there's a possibility that. For this reason, when the extreme pressure agent is used alone, the carbide coating inhibits contact between the extreme pressure agent and the metal surface, and there is a possibility that a sufficient effect of the extreme pressure agent cannot be expected.

An extreme pressure agent is used in the range of 0-10 mass% with respect to 100 mass% of lubricating oil compositions for motor vehicle transmission as needed.
Examples of the cleaning dispersant include metal sulfonates, metal phenates, metal phosphonates, and succinimides. The cleaning dispersant is used in the range of 0 to 15% by mass with respect to 100% by mass of the lubricating oil composition for an automobile transmission as necessary.

  Examples of the antiwear agent include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, polytetrafluoroethylene, and the like. 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 for an automobile transmission as necessary.

  As the friction modifier, an amine compound, an imide compound or a fatty acid having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl group or linear alkenyl group having 6 to 30 carbon atoms in the molecule. Examples include esters, fatty acid amides, fatty acid metal salts, and the like.

  Examples of the amine compound include linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or fatty acids thereof. An alkylene oxide adduct of a group amine can be exemplified. Examples of the imide compound include a succinimide having a linear or branched alkyl group or alkenyl group having 6 to 30 carbon atoms and / or a modified compound thereof using carboxylic acid, boric acid, phosphoric acid, sulfuric acid, or the like. . 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 the fatty acid metal salt include an alkaline earth metal salt (magnesium salt, calcium salt, etc.) or zinc salt of a linear or branched, preferably linear fatty acid having 7 to 31 carbon atoms.

A friction modifier is used in the range of 0-5.0 mass% with respect to 100 mass% of lubricating oil compositions for motor vehicle transmission as needed.
Antioxidants include phenolic and amine compounds such as 2,6-di-t-butyl-4-methylphenol. The antioxidant is used in the range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition for automobile transmission as required.

  Examples of the corrosion inhibitor include compounds such as benzotriazole, benzimidazole and thiadiazole. The corrosion inhibitor is used in a range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition for an automobile transmission as necessary.

  Examples of the rust preventive agent include various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, sulfonates, and the like. A rust preventive agent is used in the range of 0-3 mass% with respect to 100 mass% of lubricating oil compositions for motor vehicle transmission as needed.

  Examples of the antifoaming agent include silicone compounds such as dimethylsiloxane and silica gel dispersion, alcohol compounds and ester compounds. An antifoaming agent is used in the range of 0-0.2 mass% with respect to 100 mass% of lubricating oil compositions for motor vehicle transmission as needed.

  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. Examples of vinyl polymers containing organic acid ester groups include alkyl methacrylate (co) polymers, alkyl acrylate (co) polymers, alkyl fumarate (co) polymers, and alkyl maleate (co). Examples include polymers and alkylated naphthalene.

  Such a pour point depressant has a melting point of −13 ° C. or lower, preferably −15 ° C., more preferably −17 ° C. or lower. The melting point of the pour point depressant is measured using a differential scanning calorimeter (DSC). Specifically, about 5 mg of a 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. Thereafter, it is determined from an endothermic curve when the temperature is raised at 10 ° C./min.

  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. In the range of ~ 200,000.

The pour point depressant is used in the range of 0 to 2% by mass with respect to 100% by mass of the lubricating oil composition for an automobile transmission as necessary.
In addition to the above additives, a demulsifier, a colorant, an oily agent (oiliness improver), and the like can be used as necessary.

  In automatic transmission oils and continuously variable transmission oils, so-called DI packages, which are formulated with various necessary additives for this purpose and concentrated and dissolved in a lubricating oil such as mineral oil or synthetic hydrocarbon oil, are supplied industrially. For example, DI packages for automatic transmission oil include HITEC 3419D manufactured by AFTON CHEMICAL, HITEC 2426 manufactured by AFTON CHEMICAL, etc., and DI packages for continuously variable transmission fluid include Lubrizol 6373 manufactured by LUBRIZOL, etc. The package can also be applied to the lubricating oil composition of the present invention.

<Application>
The lubricating oil composition for automobile transmissions of the present invention can be suitably used for automobile transmission oils such as manual transmission oil, automatic transmission oil, continuously variable transmission oil, and dual clutch transmission oil, and has extremely excellent shear stability. In addition, the temperature-viscosity characteristics, the low-temperature viscosity characteristics, and the oil film retention performance are excellent and well-balanced, and can greatly contribute to the fuel-saving performance of automobiles. In particular, it can be suitably used for a dual clutch transmission oil in which a high shear stress is applied to the transmission oil and the influence of the agitation resistance by the transmission oil is large.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Evaluation method]
In the following examples and comparative examples, the physical properties and the like of the ethylene-α-olefin copolymer and the lubricating oil composition for automobile transmissions were measured by the following methods.

<Unsaturated bond amount (pieces / 1000C)>
The o- dichlorobenzene -d ₄ as a measurement solvent, measurement temperature 120 ° C., spectral width 20 ppm, pulse repetition time 7.0 sec, and at the measurement conditions of the pulse width 6.15μsec (45 ° pulse), ¹ H- NMR spectrum (400 MHz, JEOL ECX400P) was measured. The chemical shift standard uses a solvent peak (orthodichlorobenzene 7.1 ppm) and is derived from the main peak observed at 0-3 ppm and vinyl, vinylidene, disubstituted olefins and trisubstituted olefins observed at 4-6 ppm. The amount of unsaturated bonds per 1000 carbon atoms (numbers / 1000 C) was calculated from the ratio of the integrated values of the peaks.

<Ethylene 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 rolling vibration of the long chain methylene group and 1155 cm ⁻ based on the skeletal vibration of propylene absorbance ratio of the absorption of near ¹ (D1155cm ^-1 / D721cm ^-1) is calculated and prepared in advance in advance a calibration curve (prepared using a standard sample with ASTM D3900) from the ethylene content (% by weight) Asked. Next, ethylene content rate (mol%) was calculated | required according to the following formula using the obtained ethylene content rate (weight%).

<Molecular weight distribution>
The molecular weight distribution was measured as follows using Tosoh Corporation HLC-8320GPC. As a separation column, TSKgel SuperMultipore HZ-M (4) was used, the column temperature was 40 ° C., tetrahydrofuran (manufactured by Wako Pure Chemical Industries) was used as the mobile phase, the development rate was 0.35 ml / min, and the sample concentration was The amount of sample injection 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. According to the procedure of general-purpose calibration, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated as polystyrene molecular weight, and the molecular weight distribution (Mw / Mn) was calculated from these values.

<Melting point>
Using Seiko Instruments X-DSC-7000, about 8 mg of ethylene-α-olefin copolymer is placed in an aluminum sample pan that can be easily sealed and placed in the DSC cell. The temperature was raised to 150 ° C. at 10 ° C./min, and then held at 150 ° C. for 5 minutes, then the temperature was lowered at 10 ° C./min, and the DSC cell was cooled to −100 ° C. (temperature lowering 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 temperature raising process shows the maximum value is the melting point (Tm), and the total endothermic amount associated with melting is melted. The amount of heat (ΔH) was used. When no peak was observed or the value of heat of fusion (ΔH) was 1 J / g or less, it was considered that the melting point (Tm) was not observed. The method for obtaining the melting point (Tm) and the heat of fusion (ΔH) was based on JIS K7121.

<Viscosity characteristics>
The 100 ° C. kinematic viscosity and the viscosity index were measured and calculated by the method described in JIS K2283.

<Pour point>
The pour point was measured by the method described in ASTM D97. In addition, when a pour point was less than -60 degreeC, it described as -60 degrees C or less.

<Shear test>
Regarding the shear stability of the lubricating oil composition for automobile transmissions, the lubricating oil composition was tested in accordance with the method described in CRC L-45-T-93, using a KRL shear tester, with a test time of 20 Shearing was performed under shear conditions of time, a test temperature of 60 ° C., and a bearing rotational speed of 1450 rpm, and the rate of decrease in the 100 ° C. kinematic viscosity (shear test viscosity decrease rate) due to shear represented by the following formula was evaluated.
Shear test viscosity reduction rate (%) = (100 ° C. kinematic viscosity before shearing−100 ° C. kinematic viscosity after shearing) / 100 ° C. kinematic viscosity before shearing × 100

<-40 ° C viscosity>
As a low temperature viscosity characteristic, -40 degreeC viscosity was measured with the Brookfield viscometer at -40 degreeC, respectively based on ASTMD2983. When the speed is 20,000 mPa · s or less, the transmission operates well even at low temperatures.

[Production of ethylene-α-olefin copolymer (B)]
The ethylene-α-olefin copolymer (B) was produced according to the following polymerization example. In addition, about the obtained ethylene-alpha-olefin copolymer (B), hydrogenation operation was implemented by the following method as needed.

<Hydrogenation operation>
To a stainless steel autoclave with an internal volume of 1 L, 100 mL of a hexane solution of 0.5 mass% Pd / alumina catalyst and 500 mL of a 30 mass% hexane solution of an ethylene-α-olefin copolymer were added, and the autoclave was sealed and then purged with nitrogen. It was. Next, the temperature was raised to 140 ° C. with stirring, and the inside of the system was replaced with hydrogen. Then, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was performed for 15 minutes.

<Synthesis of metallocene compounds>
[Synthesis Example 1]
[Methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] Synthesis of zirconium dichloride (i) Synthesis of 6-methyl-6-phenylfulvene Nitrogen atmosphere Under a 200 mL three-necked flask, 7.3 g (101.6 mmol) of lithium cyclopentadiene and 100 mL of dehydrated tetrahydrofuran were added and stirred. The solution was cooled in an ice bath and 15.0 g (111.8 mmol) of acetophenone was added dropwise. Then, it stirred at room temperature for 20 hours and the obtained solution was quenched with dilute hydrochloric acid aqueous solution. Hexane 100mL was added and the soluble part was extracted, and this organic layer was dried with anhydrous magnesium sulfate after washing | cleaning with water and a saturated salt solution. 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) Synthesis of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane 2,7-di-t-butylfluorene in a 100 mL three-necked flask under a nitrogen atmosphere 01 g (7.20 mmol) and 50 mL of dehydrated t-butyl methyl ether were added. While cooling with an ice bath, 4.60 mL (7.59 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added, 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 for 1 hour with heating under reflux. While cooling with an ice bath, 50 mL of water was gradually added, and the resulting bilayer 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 3 times with 50 mL of water and once with 50 mL of saturated brine. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. When ultrasonic waves were applied to the solution obtained by adding a small amount of hexane, a solid was 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) Synthesis of [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride In a nitrogen atmosphere, methyl (cyclopenta) was added to a 100 mL Schlenk tube. 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. While cooling in an ice bath, 4.20 mL (6.93 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added, 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 warming to room temperature, whereby a red-orange slurry was obtained. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and extracted with dichloromethane. After evaporating the solvent under reduced pressure and concentrating, a small amount of hexane was added and the mixture was allowed to stand at −20 ° C. to precipitate a red-orange solid. The 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-butylfull] as a red-orange solid. Olenyl)] 1.20 g of zirconium dichloride was obtained.

[Synthesis Example 2]
Ethylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,7-di -t- butyl-fluorenyl) Synthesis of zirconium dichloride Ethylene (eta ⁵ - cyclopentadienyl) (η ⁵ -2, 7-di-t-butylfluorenyl)] zirconium dichloride was synthesized by the method described in Japanese Patent No. 4367687.

<Polymerization example 1>
By charging 710 mL of heptane and 95 g of propylene into a 2 L stainless steel autoclave sufficiently purged with nitrogen, raising the temperature inside the system to 150 ° C., and then supplying hydrogen 1.34 MPa and ethylene 0.32 MPa The total pressure was 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride 0.0001 mmol and N, N— Polymerization was initiated by injecting 0.001 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring speed to 400 rpm. Thereafter, 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 the polymerization was stopped by adding a small amount of ethanol to the system, unreacted ethylene, propylene and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000 mL of 0.2 mol / l hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained polymer was dried overnight under reduced pressure at 80 ° C. to obtain 52.2 g of an ethylene-propylene copolymer. Further, this ethylene-propylene copolymer was subjected to a hydrogenation operation.

The polymer (polymer 1) obtained by the above operation has an unsaturated bond content of less than 0.1 / 1000 C, an ethylene content of 61.0 mol%, Mw / Mn of 2.0, and a 100 ° C. kinematic viscosity of 1 , 060 mm ² / s, the melting point (melting peak) was −38 ° C., and the heat of fusion was 5.8 J / g.

<Polymerization example 2>
An ethylene-propylene copolymer (polymer 2) having a colorless and transparent appearance was obtained by the same operation as in Polymerization Example 1 except that 90 g of propylene was charged and hydrogen 1.35 MPa and ethylene 0.34 MPa were supplied. Further, this ethylene-propylene copolymer was subjected to a hydrogenation operation.

The polymer (polymer 2) obtained by the above operation has an unsaturated bond amount of less than 0.1 / 1000 C, an ethylene content of 64.5 mol%, an Mw / Mn of 2.0, and a 100 ° C. kinematic viscosity of 1. a 000 mm ² / s, a melting point (melting peak) is -35 ° C., a heat of fusion was 9.5J / g.

<Polymerization Example 3>
An ethylene-propylene copolymer (polymer 3) having a colorless and transparent appearance was obtained by the same operation as in Polymerization Example 1 except that 100 g of propylene was charged and hydrogen 1.33 MPa and ethylene 0.29 MPa were supplied. Further, this ethylene-propylene copolymer was subjected to a hydrogenation operation.

The polymer (polymer 3) obtained by the above operation has an unsaturated bond content of less than 0.1 / 1000 C, an ethylene content of 53.1 mol%, an Mw / Mn of 1.9, and a 100 ° C. kinematic viscosity of 1. , 120 mm ² / s, and no melting point was observed.

<Polymerization example 4>
By charging 910 mL of heptane and 45 g of propylene into a 2 L stainless steel autoclave sufficiently purged with nitrogen, raising the temperature in the system to 130 ° C., and then supplying 2.17 MPa of hydrogen and 0.15 MPa of ethylene The total pressure was 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride 0.0006 mmol 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, by continuously supplying only ethylene, the total pressure was kept at 3 MPaG, and polymerization was carried out at 130 ° C. for 5 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, unreacted ethylene, propylene and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000 mL of 0.2 mol / l hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained polymer was dried overnight at 80 ° C. under reduced pressure, and further, using a 2-03 type thin film distillation apparatus manufactured by Shinko Pantech, the degree of vacuum was maintained at 400 Pa, a set temperature of 180 ° C., and a flow rate of 3.1 ml. Thin film distillation was performed at / min to obtain 22.2 g of an ethylene-propylene copolymer whose appearance was colorless and transparent. Further, this ethylene-propylene copolymer was subjected to a hydrogenation operation.

The polymer (polymer 4) obtained by the above operation has an unsaturated bond content of less than 0.1 / 1000 C, an ethylene content of 66.1 mol%, Mw / Mn of 1.6, and a 100 ° C. kinematic viscosity of 80 mm. ^The melting point (melting peak) was −33 ° C., and the heat of fusion was 19.8 J / g.

[Preparation of lubricating oil composition for automobile transmission]
Components other than the ethylene-α-olefin copolymer (B) used in the preparation of the following lubricating oil composition for automobile transmissions are as follows.
Mineral oil: GTL (Gas to Liquid) mineral oil (Resella X415 manufactured by Shell, Mineral oil-A) having a kinematic viscosity of 100 mm at 2.6 ° C. of 2.6 mm ² / s, a viscosity index of 118, and a pour point of −39 ° C., 100 An API (American Petroleum Institute) Group II mineral oil (NEXBASE3030, Mineral Oil-B) having a kinematic viscosity of 3.0 mm ² / s, a viscosity index of 106, and a pour point of −30 ° C.
DI package; HITEC-3419D (DI) manufactured by Afton Chemical
Pour point depressant; IRGAFLO 720P (PPD) manufactured by BASF
PAO; Spectrasyn Elite 65 (mPAO) manufactured by ExxonMobil Chemical manufactured with a metallocene catalyst system having a kinematic viscosity of 100 ° C. of 65 mm ² / s and a viscosity index of 179

<Lubricating oil composition for automobile transmission>
In Example 1, Example 2, and Comparative Examples 1-5, it shows in Table 3 so that the 100 degreeC kinematic viscosity of a lubricating oil composition may exceed 5.5 mm < ² > / s as a lubricating oil composition for motor vehicle transmissions. Mixing adjustment was performed with the mixing ratio. The lubricating oil properties of the resulting lubricating oil composition are also shown in Table 3.

The lubricating oil compositions of Example 1 and Example 2 containing the mineral oil (A) and the ethylene-α-olefin copolymer (B) both have a kinematic viscosity at 40 ° C. lower than 25 mm ² / s at the start. This is a lubricating oil composition that has excellent fuel economy because of low stirring resistance to the transmission, and excellent low-temperature fluidity and shear stability.

On the other hand, in Comparative Examples 1 and 2 in which the viscosity index of the mineral oil (A) is less than 110, the 40 ° C. kinematic viscosity of the lubricating oil composition exceeds 25 mm ² / s, and the fuel efficiency deteriorates. Further, from Comparative Example 3, the 100 ° C. kinematic viscosity of the ethylene-α-olefin copolymer (B) is 200 mm ² / s or more, whereby the 40 ° C. kinematic viscosity can be suppressed to 25 mm ² / s or less, and the low temperature viscosity. It can be seen that the characteristics are also excellent.
Further, it can be seen from Comparative Example 5 that the lubricating oil composition has a kinematic viscosity at 100 ° C. of 9.0 mm ² / s, which is preferable in terms of fluidity at low temperatures and in terms of shear stability.

Claims (4)

Lubricating oil base oil containing mineral oil (A) having the following characteristics (A1) to (A3), and ethylene-α-olefin copolymer (B) having the following characteristics (B1) to (B5) An automotive transmission lubricating oil composition having a kinematic viscosity at 100 ° C. of 4.0 to 9.0 mm ² / s.
(A1) Kinematic viscosity at 100 ° C. is 2.0 to 6.5 mm ² / s (A2) Viscosity index is 105 or more (A3) Pour point is −10 ° C. or less (B1) Ethylene (B2) Kinematic viscosity at 100 ° C. is 200 to 3,000 mm ² / s (B3) 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 (B4) The pour point is 0 ° C. or less (B5) from −30 ° C. in the differential scanning calorimetry (DSC) measurement. It has a peak in the range of −60 ° C. and a melting point with a heat of fusion (ΔH) of 25 J / g or less.   The lubricating oil composition for an automobile transmission according to claim 1, wherein the ethylene content of the ethylene-α-olefin copolymer (B) is in the range of 58 to 70 mol%. 3. The lubricating oil composition for an automobile transmission according to claim 1, wherein the ethylene-α-olefin copolymer (B) has a kinematic viscosity at 100 ° C. of 500 to 2,500 mm ² / s.   The lubricating oil composition for an automobile transmission according to any one of claims 1 to 3, wherein the α-olefin of the ethylene-α-olefin copolymer (B) is propylene.