[0001]The present invention relates to a lubricating oil 10 composition for internal combustion engines and a method for
producing the same, and particularly relates to a lubricating oil composition for high-output internal combustion engines and a process for producing the same.
15 Background Art [0002]
Petroleum products generally have the so-called viscosity temperature dependency, in which viscosity varies greatly with temperature change. For example, in lubricating
20 oil and the like, which is used in automobiles etc., a small viscosity temperature dependency is preferred. Thus, in lubricating oil, certain types of polymers soluble in lubricating oil bases have been utilized as viscosity modifying agents (also called viscosity index improving

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agents), with the objective of reducing the viscosity temperature dependency. In recent years, OCPs (olefin copolymers) have been widely utilized as such viscosity modifying agents, and there have been a variety of 5 improvements to OCP in order to further improve the
performance of lubricating oil, as exemplified in Patent
Literature 1.
[0003]
Meanwhile, amidst the increased demands in recent years
10 for a reduction in environmental burden, there is strong
demand for improvements in the fuel consumption of internal combustion engines. Fuel consumption improvement technology of engine oil is one of such countermeasures, where the lowering of the viscosity of engine oil has been in progress,
15 with the objective of reducing torque in regular automobiles by the lowered viscosity. However, since engine pistons and cranks bear huge loads in high-output type engines such as large displacement engines for construction machinery and heavy machinery, or crosshead type diesel engines oil for
20 ocean vessels, a high viscosity engine oil of 40 or more
according to the viscosity standard established by the SAE (Society of Automotive Engineers) as shown in Table 1 is often utilized with the objective of protecting these engine parts, and lowering the viscosity is difficult. Moreover, the

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engines of regular- and two-wheeled automobiles for racing, or the engines of large displacement two-wheeled automobiles such as large-sized two-wheelers are also used in a higher-revving domain, compared to that of regular automobiles and 5 compact, mid-sized two-wheelers. Here, a high viscosity
engine oil is utilized because the temperature of the engine oil becomes higher, which leads to viscosity reduction. [0004]
Viscosity index improving agents are utilized in engine
10 oil so that the lubricating oil maintains an optimal
viscosity at high temperatures. However, the molecular weight of general viscosity index improving agents used in engine oil for regular automobiles is comparatively high, and thus molecular cleaving occurs due to shear stress, which tends to
15 cause viscosity reduction of the lubricating oil. It is thus particularly unsuitable to utilize general viscosity index improving agents in high viscosity engine oil used in the aforementioned harsh conditions. Therefore, viscosity modifying agents of comparatively low molecular weight are
20 utilized. However, even though viscosity reduction due to
shearing can be suppressed, the viscosity index improvement performance worsens. Thus, the viscosity temperature
dependency increases, the fluidity of lubricating oil becomes poor under a low-temperature environment; specifically at

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40°C or lower, and agitation resistance when starting an internal combustion engine becomes remarkably great compared to that of the engine oil for regular automobiles, all of which badly affects the fuel consumption of internal 5 combustion engines. [0005]
Patent Literature 2 discloses a lubricating oil composition having a low temperature dependence of viscosity; namely, having an excellent fluidity at -40°C or lower, while
10 maintaining high shear stability, and having low agitation resistance in an engine, which is suitably applicable to internal combustion engines, where the lubricating oil composition contains a specific lubricant base oil and a specific ethylene-α-olefin copolymer.
15 [0006]
Moreover, Patent Literature 3 describes a method for producing a liquid random copolymer of ethylene and α-olefin, wherein further described is that this copolymer is useful as a lubricating oil.
20 [0007]

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5

Table 1

Viscosity standard *1 CCS Viscosity *2 MR viscosity *3 Kinematic viscosity at 100°C *4 HTHS viscosity *5
Measured temperature Upper limit viscosity Measured temperature Upper limit viscosity Lower limit viscosity Upper limit viscosity Lower limit viscosity
°C mPa･s °C mPa･s mm2/s mm2/s mPa･s
5 W 30 6,600 35 60,000 3.8
10 W - 25 7,000 - 30 60,000 4.1
15 W - 20 7,000 - 25 60,000 5.6
20 W - 15 9,500 - 20 60,000 5.6
25 W - 10 13,000 - 15 60,000 9.3
40 Not prescribed 12.5 < 16.3 3.5 *6 3.7 *7
50
16.3 < 21.9 3.7
60 21.9 < 26.1 3.7
*1: Gear oils which satisfy two viscosity standards in the table are described as multi-grade gear oil with both viscosity standards. For example, the description 5W-40 is indicated when the standards 5W and 40 in the table are satisfied.

5

*2: Measured in accordance with ASTM D5293

*3: Measured in accordance with ASTM D4684
*4: Measured in accordance with ASTM D445
*5: Measured in accordance with ASTM D4683
*6: For 5W-40 or 10W-40

10

*7: For any of 15W-40, 20W-40, 25W-40

Citation List
Patent Literature
[0008]

15

Patent Literature 1: WO 00/034420 A1

Patent Literature 2: JP 2016-098342 A
Patent Literature 3: EP 2921509 A
Summary of Invention

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Technical Problem [0009]
However, there was further room for improvement in conventional lubricating oil compositions, from the 5 perspective of providing a lubricating oil composition for internal combustion engines having a low temperature
dependence of viscosity; namely, having an excellent fluidity under a low-temperature environment, while maintaining high shear stability, having low agitation resistance in an 10 engine, and further having excellent thermal and oxidation stability.
Solution to Problem [0010]
15 The present inventors keenly investigated the
development of a lubricating oil composition having excellent performance, and as a result, discovered that the
aforementioned problem can be solved with a lubricating oil composition which contains, with a specific lubricant base
20 oil, an ethylene-α-olefin copolymer prepared by means of a specific catalyst, and satisfies specific conditions, thus arriving at the perfection of the present invention. The present invention specifically mentions the below aspect. [0011]

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[1]
A lubricating oil composition for internal combustion
engines, comprising a lubricant base oil, and a liquid random
copolymer (C) of ethylene and α-olefin, the liquid random 5 copolymer (C) being prepared by the below method (α), the
lubricating oil composition having a kinematic viscosity at
100°C of 12.5 mm2/s or more, but less than 26.1 mm2/s,
wherein the lubricant base oil consists of a mineral
oil (A) having the properties of the below (A1) to (A3), 10 and/or a synthetic oil (B) having the properties of the below
(B1) to (B3).
(A1) The mineral oil has a kinematic viscosity at 100°C of 2
to 10 mm2/s.
(A2) The mineral oil has a viscosity index of 95 or more. 15 (A3) The mineral oil has a pour point of -10°C or lower.
(B1) The synthetic oil has a kinematic viscosity at 100°C of
1 to 10 mm2/s.
(B2) The synthetic oil has a viscosity index of 120 or more.
(B3) The synthetic oil has a pour point of -30°C or lower. 20 (Method (α))
A method (α) for preparing a liquid random copolymer of
ethylene and α-olefin, comprising a step of carrying out
solution polymerization of ethylene and α-olefin having 3 to
20 carbon atoms, under a catalyst system comprising

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(a) a bridged metallocene compound represented by the following Formula 1, and
(b) at least one compound selected from a group consisting of
(i) an organoaluminum oxy-compound, and
5 (ii) a compound which reacts with the bridged
metallocene compound to form an ion pair. [0012]

(Formula 1)
[In Formula 1, R1, R2, R3, R4, R5, R8, R9 and R12 are 10 respectively and independently hydrogen atom, hydrocarbon
group or silicon-containing hydrocarbon group, and adjoining groups are optionally connected to each other to form a ring structure,
R6 and R11, being the same, are hydrogen atom,

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hydrocarbon group or silicon-containing hydrocarbon group,
R7 and R10, being the same, are hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group,
R6 and R7 are optionally connected to hydrocarbon having 5 2 to 3 carbon atoms to form a ring structure,
R11 and R10 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,
R6, R7, R10 and R11 are not hydrogen atom at the same
time;
10 Y is a carbon atom or silicon atom;
R13 and R14 are independently aryl group;
M is Ti, Zr or Hf;
Q is independently halogen, hydrocarbon group, an anionic ligand or a neutral ligand which can be coordinated 15 to a lone pair of electrons; and
j is an integer of 1 to 4.] [2]
The lubricating oil composition for internal combustion engines of the aforementioned [1], wherein in the metallocene 20 compound represented by the above Formula 1, at least one among substituents (R1, R2, R3 and R4) bonded to a cyclopentadienyl group is a hydrocarbon group having 4 or more carbon atoms. [0013]

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[3]
The lubricating oil composition for internal combustion
engines of the aforementioned [1] or [2], wherein R6 and R11,
being the same, are hydrocarbon groups having 1 to 20 carbon 5 atoms.
[0014]
[4]
The lubricating oil composition for internal combustion
engines of any of the aforementioned [1] to [3], wherein in 10 the metallocene compound represented by the above Formula 1,
substituent (R2 or R3) bonded to the 3-position of the
cyclopentadienyl group is a hydrocarbon group.
[0015]
[5]
15 The lubricating oil composition for internal combustion
engines of the aforementioned [4], wherein in the metallocene
compound represented by the above Formula 1, the hydrocarbon
group (R2 or R3) bonded to the 3-position of the
cyclopentadienyl group is an n-butyl group. 20 [0016]
[6]
The lubricating oil composition for internal combustion
engines of any of the aforementioned [1] to [5], wherein in
the metallocene compound represented by the above Formula 1,

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substituents (R6 and R11) bonded to the 2-position and 7-position of the fluorenyl group are all tert-butyl groups. [0017] [7] 5 The lubricating oil composition for internal combustion engines of any of the aforementioned [1] to [6], wherein the compound which reacts with the bridged metallocene compound to form an ion pair is a compound represented by the following Formula 6. 10 [0018]
Rg pe R B—R
R ., ■■■ (Formula 6)
[In Formula 6, Re+ is H+, a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a
15 transition metal, and Rf to Ri each is independently a hydrocarbon group having 1 to 20 carbon atoms.] [8]
The lubricating oil composition for internal combustion engines of the aforementioned [7], wherein the ammonium
20 cation is a dimethylanilinium cation. [0019]

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[9]
The lubricating oil composition for internal combustion engines of the aforementioned [7] or [8], wherein the catalyst system further comprises an organoaluminum compound 5 selected from a group consisting of trimethyl aluminum and triisobutyl aluminum. [0020] [10]
The lubricating oil composition for internal combustion 10 engines of any of the aforementioned [1] to [9], wherein the α-olefin of the liquid random copolymer (C) is propylene. [0021]
[11]
A lubricating oil composition for internal combustion
15 engines, comprising a lubricant base oil, and a liquid random copolymer of ethylene and α-olefin, the liquid random copolymer having the properties of the below (C1) to (C5), the lubricating oil composition having a kinematic viscosity at 100°C of 12.5 mm2/s or more, but less than 26.1 mm2/s,
20 wherein the lubricant base oil consists of a mineral oil (A) having the properties of the below (A1) to (A3), and/or a synthetic oil (B) having the properties of the below (B1) to (B3). (A1) The mineral oil has a kinematic viscosity at 100°C of 2

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to 10 mm2/s.
(A2) The mineral oil has a viscosity index of 95 or more.
(A3) The mineral oil has a pour point of -10°C or lower.
(B1) The synthetic oil has a kinematic viscosity at 100°C of 5 1 to 10 mm2/s.
(B2) The synthetic oil has a viscosity index of 120 or more.
(B3) The synthetic oil has a pour point of -30°C or lower.
(C1) The liquid random copolymer comprises 40 to 60 mol% of
ethylene units and 60 to 40 mol% of α-olefin units having 3 10 to 20 carbon atoms.
(C2) The liquid random copolymer has a number average
molecular weight (Mn) of 500 to 10,000 and a molecular weight
distribution (Mw/Mn, Mw is the weight average molecular
weight) of 3 or less, as measured by Gel Permeation 15 Chromatography (GPC).
(C3) The liquid random copolymer has a kinematic viscosity at
100°C of 30 to 5,000 mm2/s.
(C4) The liquid random copolymer has a pour point of 30
to -45°C. 20 (C5) The liquid random copolymer has a Bromine Number of 0.1
g / 100 g or less.
[12]
The lubricating oil composition for internal combustion
engines of any of the aforementioned [1] to [11], wherein the

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synthetic oil (B) contains an ester, and a synthetic oil
other than ester.
[0022]
[13]
5 The lubricating oil composition for internal combustion
engines of any of the aforementioned [1] to [12], having a
total base value of at least 20 mg-KOH/g.
[0023]
[14]
10 A diesel engine oil, consisting of the lubricating oil
composition for internal combustion engines of any of the
aforementioned [1] to [13].
[0024]
[15]
15 A method for producing a lubricating oil composition
for internal combustion engines, comprising the steps of:
preparing a liquid random copolymer (C) of ethylene and
α-olefin by the following method (α); and
preparing a lubricating oil composition for internal 20 combustion engines by mixing a lubricant base oil and the
liquid random copolymer (C), the composition having a
kinematic viscosity at 100°C of 12.5 mm2/s or more, but less
than 26.1 mm2/s,
wherein the lubricant base oil consists of a mineral

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15
oil (A) having the properties of the below (A1) to (A3),
and/or a synthetic oil (B) having the properties of the below
(B1) to (B3).
(A1) The mineral oil has a kinematic viscosity at 100°C of 2 5 to 10 mm2/s.
(A2) The mineral oil has a viscosity index of 95 or more.
(A3) The mineral oil has a pour point of -10°C or lower.
(B1) The synthetic oil has a kinematic viscosity at 100°C of
1 to 10 mm2/s. 10 (B2) The synthetic oil has a viscosity index of 120 or more.
(B3) The synthetic oil has a pour point of -30°C or lower.
(Method (α))
A method (α) for preparing a liquid random copolymer of
ethylene and α-olefin, comprising a step of carrying out 15 solution polymerization of ethylene and α-olefin having 3 to
20 carbon atoms, under a catalyst system comprising
(a) a bridged metallocene compound represented by the
following Formula 1, and
(b) at least one compound selected from a group consisting of
20 (i) an organoaluminum oxy-compound, and
(ii) a compound which reacts with the bridged metallocene compound to form an ion pair. [0025]

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16


(Formula 1)
[In Formula 1, R1, R2, R3, R4, R5, R8, R9 and R12 are respectively and independently hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group, and adjoining 5 groups are optionally connected to each other to form a ring structure,
R6 and R11, being the same, are hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group,
R7 and R10, being the same, are hydrogen atom, 10 hydrocarbon group or silicon-containing hydrocarbon group,
R6 and R7 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,
R11 and R10 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,

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R6, R7, R10 and R11 are not hydrogen atom at the same time;
Y is a carbon atom or silicon atom;
R13 and R14 are independently aryl group;
5 M is Ti, Zr or Hf;
Q is independently halogen, hydrocarbon group, an anionic ligand or a neutral ligand which can be coordinated to a lone pair of electrons; and
j is an integer of 1 to 4.] 10
Advantageous Effects of Invention [0026]
The lubricating oil composition of the present invention maintains high shear stability, and exhibits 15 remarkably excellent temperature viscosity properties and excellent low-temperature fluidity. The lubricating oil composition further has excellent thermal and oxidation stability, and contributes to better fuel efficiency of internal combustion engine oil. 20
Description of Embodiments [0027]
The lubricating oil composition for internal combustion engines according to the present invention (hereinafter, also

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referred to merely as “lubricating oil composition”) will be
explained in detail below.
[0028]
The lubricating oil composition for internal combustion 5 engines according to the present invention comprises a
lubricant base oil, and a liquid random copolymer (C) of
ethylene and α-olefin prepared by method (α) (may also be
described in the present specification as “ethylene-α-olefin
copolymer (C)”), the lubricating oil composition having a 10 kinematic viscosity at 100°C of 12.5 mm2/s or more, but less
than 26.1 mm2/s, where the lubricant base oil consists of a
mineral oil (A) and/or synthetic oil (B).
[0029]
< Lubricant base oil > 15 In the lubricant base oil used in the present
invention, performance and quality such as viscosity
properties, heat resistance and oxidation stability, will
differ depending on the producing and refining processes etc.
of the lubricant base oil. The API (American Petroleum 20 Institute) categorizes lubricant base oil into five types:
Group I, II, III, IV and V. These API categories are defined
in the API Publication 1509, 15th Edition, Appendix E, April
2002, and are as shown in Table 2.
[0030]

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Table 2

Group Type Viscosity index *1 Saturated
hydrocarbon
portion *2
(vol%) Sulfur
portion *3 (%
by weight)
I Mineral oil 80 to 120 < 90 > 0.03
II Mineral oil 80 to 120 ≥ 90 ≤ 0.03
III Mineral oil ≥ 120 ≥ 90 ≤ 0.03
IV Poly-a-olefin
V Lubricant base material other than the aforementioned
*1: Measured in accordance with ASTM D445 (JIS K2283)
*2: Measured in accordance with ASTM D3238
*3: Measured in accordance with ASTM D4294 (JIS K2541) 5 *4: Mineral oils whose saturated hydrocarbon portion is less
than 90 vol% and sulfur portion is less than 0.03% by weight, or whose saturated hydrocarbon portion is 90 vol% or more and sulfur portion exceeds 0.03% by weight, are included in Group I.
10
< Mineral oil (A) >
The mineral oil (A) has the properties of (A1) to (A3) below. The mineral oil (A) in the present invention is ascribed to Groups I to III of the aforementioned API
15 categories. [0031]

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(A1) The mineral oil has a kinematic viscosity at 100°C of 2 to 10 mm2/s
The value of this kinematic viscosity is that as measured in accordance with the method described in JIS 5 K2283. The kinematic viscosity at 100°C of mineral oil (A) is 2 to 10 mm2/s, preferably 2.5 to 8 mm2/s, and more preferably 3.5 to 6.5 mm2/s. With a kinematic viscosity at 100°C in this range, the lubricating oil composition of the present invention is excellent in terms of volatility and temperature
10 viscosity properties. [0032] (A2) The mineral oil has a viscosity index of 95 or more
The value of this viscosity index is that as measured in accordance with the method described in JIS K2283. The
15 viscosity index of mineral oil (A) is 95 or more, preferably 105 or more, and more preferably 120 or more. With a viscosity index in this range, the lubricating oil composition of the present invention has excellent temperature viscosity properties.
20 [0033]
(A3) The mineral oil has a pour point of -10°C or lower
The value of this pour point is that as measured in accordance with the method described in ASTM D97. The pour point of mineral oil (A) is -10°C or lower, and

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preferably -12°C or lower. With a pour point in this range, the lubricating oil composition of the present invention has excellent low-temperature viscosity properties, when using the mineral oil (A) together with a pour point lowering 5 agent. [0034]
The quality of the mineral oil is as mentioned above, where the aforementioned respective qualities of mineral oil are obtainable depending on the refining method.
10 Exemplifications of the mineral oil (A) specifically include: a lubricant base oil, in which a lubricating oil fraction obtained by reduced pressure distillation of an atmospheric residue which is obtainable by the atmospheric distillation of crude oil, is refined by one or more treatments such as
15 solvent deasphalting, solvent extraction, hydrocracking,
solvent dewaxing, hydrorefining; or a lubricant base oil of
wax isomerized mineral oil.
[0035]
Moreover, a Gas-to-Liquid (GTL) base oil obtained by
20 the Fisher-Tropsch method is a base oil which can also be
suitably utilized as Group III mineral oil. Such GTL base oil is also handled as Group III+ lubricant base oil, which are described e.g. in the following Patent Literatures: EP0776959, EP0668342, WO97/21788, WO00/15736, WO00/14188,

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WO00/14187, WO00/14183, WO00/14179, WO00/08115, WO99/41332,
EP1029029, WO01/18156 and WO01/57166.
[0036]
In the lubricating oil composition of the present 5 invention, the mineral oil (A) may be used alone as a
lubricant base oil, or any mixture etc. of two or more
lubricating oils selected from the synthetic oil (B) and the
mineral oil (A) may be used as a lubricant base oil.
[0037] 10 < Synthetic oil (B) >
The synthetic oil (B) has the characteristics of (B1)
to (B3) below. The synthetic oil (B) in the present invention
is ascribed to Group IV or Group V in the aforementioned API
categories. 15 [0038]
(B1) The synthetic oil has a kinematic viscosity at 100°C of
1 to 10 mm2/s
The value of this kinematic viscosity is that as
measured in accordance with the method described in JIS 20 K2283. The kinematic viscosity at 100°C of synthetic oil (B)
is 1 to 10 mm2/s, preferably 2 to 8 mm2/s, and more preferably
3.5 to 6 mm2/s. With a kinematic viscosity at 100°C in this
range, the lubricating oil composition of the present

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invention is excellent in terms of volatility and temperature viscosity properties. [0039]
(B2) The synthetic oil has a viscosity index of 120 or more 5 The value of this viscosity index is that as measured in accordance with the method described in JIS K2283. The viscosity index of synthetic oil (B) is 120 or more, and preferably 125 or more. With a viscosity index in this range, the lubricating oil composition of the present invention has
10 excellent temperature viscosity properties. [0040]
(B3) The synthetic oil has a pour point of -30°C or lower The value of this pour point is that as measured in accordance with the method described in ASTM D97. The pour
15 point of synthetic oil (B) is -30°C or lower,
preferably -40°C or lower, more preferably -50°C or lower, and furthermore preferably -60°C or lower. With a pour point in this range, the lubricating oil composition of the present invention has excellent low-temperature viscosity properties.
20 [0041]
Poly-α-olefins, which are ascribed to Group IV, can be obtained by oligomerizing higher α-olefins with an acid catalyst, as described in e.g. US Patent 3,780,128, US Patent 4,032,591, and JP H01-163136 A. Of these, a low molecular

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weight oligomer of at least one olefin selected from an olefin having 8 or more carbon atoms can be utilized as the poly-α-olefin. If utilizing a poly-α-olefin as the lubricant base oil, a lubricating oil composition having remarkably 5 excellent temperature viscosity properties, low-temperature viscosity properties, as well as heat resistance is obtainable. [0042]
Poly-α-olefins are also industrially available, where
10 those with a 100°C kinematic viscosity of 2 mm2/s to 10 mm2/s are commercially available. Examples include the NEXBASE 2000 series (made by NESTE), Spectrasyn (made by ExxonMobil Chemical), Durasyn (made by INEOS Oligomers), and Synfluid (made by Chevron Phillips Chemical).
15 [0043]
As the synthetic oil ascribed to Group V, examples include alkyl benzenes, alkyl naphthalenes, isobutene oligomers and hydrides thereof, paraffins, polyoxy alkylene glycol, dialkyl diphenylether, polyphenylether, and esters.
20 [0044]
Most of the alkyl benzenes and alkyl naphthalenes are usually dialkyl benzene or dialkyl naphthalene whose alkyl chain length has 6 to 14 carbon atoms, where such alkyl benzenes or alkyl naphthalenes are produced by the Friedel–

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Crafts alkylation reaction of benzene or naphthalene with olefin. In the production of alkyl benzenes or alkyl naphthalenes, the alkylated olefin to be utilized may be a linear or branched olefin, or may be a combination of these. 5 These production processes are described in e.g. US Patent 3,909,432. [0045]
Moreover, as the ester, fatty acid esters are preferred from the perspective of compatibility with the ethylene-α-10 olefin copolymer (C). [0046]
Although there are no particular limitations on the fatty acid esters, examples include fatty acid esters consisting of only carbon, oxygen or hydrogen as mentioned 15 below, where the examples include monoesters prepared from a monobasic acid and alcohol; diesters prepared from dibasic acid and alcohol, or from a diol with a monobasic acid or an acid mixture; or polyolesters prepared by reacting a monobasic acid or an acid mixture with a diol, triol (e.g. 20 trimethylolpropane), tetraol (e.g. pentaerythritol), hexol (e.g. dipentaerythritol) etc. Examples of these esters include ditridecyl glutarate, di-2-ethyl hexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethyl hexyl sebacate, tridecyl pelargonate, di-2-ethyl hexyl adipate, di-

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2-ethyl hexyl azelate, trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane triheptanoate, pentaerythritol-2-ethyl hexanoate, pentaerythritol pelargonate, and pentaerythritol 5 tetraheptanoate. [0047]
From the perspective of the compatibility with the ethylene-α-olefin copolymer (C), an alcohol having two or more functional hydroxyl groups is preferred as the alcohol
10 moiety constituting the ester, and a fatty acid having 8 or more carbon atoms is preferred as the fatty acid moiety. However, a fatty acid having 20 or fewer carbon atoms, which is easily industrially available, is superior in terms of the manufacturing cost of the fatty acid. The effect of the
15 present invention is also sufficiently exhibited with the use of one fatty acid constituting an ester, or with the use of a fatty acid ester prepared by means of two or more acid mixtures. Examples of fatty acid esters more specifically include a mixed triester of trimethylolpropane with lauric
20 acid and stearic acid, and diisodecyl adipate, where these are preferable in terms of compatibility of saturated hydrocarbon components such as the ethylene-α-olefin copolymer (C), with antioxidants, corrosion preventing agents, anti-wear agents, friction modifying agents, pour

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point lowering agents, anti-rust agents and anti-foamers
mentioned below and having a polar group.
[0048]
When utilizing a synthetic oil (B), particularly a 5 poly-α-olefin as a lubricant base oil, it is preferable that the lubricating oil composition of the present invention contain a fatty acid ester in an amount of 5 to 20% by mass with respect to 100% by mass of the entire weight of the lubricating oil composition. By containing a fatty acid ester
10 of 5% by mass or more, good compatibility is obtainable with the lubricating oil sealing material such as resins and elastomers inside the internal combustion engines and industrial machinery of all types. Specifically, swelling of the lubricating oil sealing material can be suppressed. From
15 the perspective of oxidation stability or heat resistance,
the amount of ester is preferably 20% by mass or less. When mineral oil is contained in the lubricating oil composition, a fatty acid ester is not necessarily required, because the mineral oil per se has a swelling suppression effect of the
20 lubricating oil sealing agent. [0049] < (C) Ethylene-α-olefin copolymer >

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The ethylene-α-olefin copolymer (C) is a liquid random copolymer (C) of ethylene and α-olefin prepared by the following method (α). (Method (α)) 5 A method (α) for preparing a liquid random copolymer of ethylene and α-olefin, comprising a step of carrying out solution polymerization of ethylene and α-olefin having 3 to 20 carbon atoms, under a catalyst system containing
(a) a bridged metallocene compound represented by the 10 following Formula 1, and
(b) at least one compound selected from a group consisting of
(i) an organoaluminum oxy-compound, and (ii) a compound which reacts with the bridged metallocene compound to form an ion pair. 15 [0050]

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29


(Formula 1)
[In Formula 1, R1, R2, R3, R4, R5, R8, R9 and R12 are respectively and independently hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group, and adjoining 5 groups are optionally connected to each other to form a ring structure,
R6 and R11, being the same, are hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group,
R7 and R10, being the same, are hydrogen atom, 10 hydrocarbon group or silicon-containing hydrocarbon group,
R6 and R7 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,
R11 and R10 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,

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R6, R7, R10 and R11 are not hydrogen atom at the same time;
Y is a carbon atom or silicon atom;
R13 and R14 are independently aryl group;
5 M is Ti, Zr or Hf;
Q is independently halogen, hydrocarbon group, an anionic ligand or a neutral ligand which can be coordinated to a lone pair of electrons; and
j is an integer of 1 to 4.]
10 Here, the hydrocarbon group has 1 to 20 carbon atoms,
preferably 1 to 15 atoms, and more preferably 4 to 10 carbon atoms, and means for example an alkyl group, aryl group etc. The aryl group has 6 to 20 carbon atoms, and preferably 6 to 15 carbon atoms. 15 [0051]
Examples of the silicon-containing hydrocarbon group include an alkyl or aryl group having 3 to 20 carbon atoms which contains 1 to 4 silicon atoms, and in more detail includes trimethylsilyl group, tert-butyldimethylsilyl group, 20 triphenylsilyl group etc. [0052]
In the bridged metallocene compound represented by Formula 1, cyclopentadienyl group may be substituted or unsubstituted.

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31
[0053]
In the bridged metallocene compound represented by Formula 1,
(i) it is preferable that at least one among 5 substituents (R1, R2, R3 and R4) bonded to cyclopentadienyl group is a hydrocarbon group,
(ii) it is more preferable that at least one among
substituents (R1, R2, R3 and R4) is a hydrocarbon group having
4 or more carbon atoms,
10 (iii) it is most preferable that substituent (R2 or R3)
bonded to the 3-position of the cyclopentadienyl group is a
hydrocarbon group having 4 or more carbon atoms (for example
an n-butyl group).
[0054]
15 In case where at least two among R1, R2, R3 and R4 are
substituents (that is, being not hydrogen atom), the above-mentioned substituents may be the same or be different, and it is preferable that at least one substituent is a hydrocarbon group having 4 or more carbon atoms. 20 [0055]
In the metallocene compound represented by Formula 1, R6 and R11 bonded to fluorenyl group are the same, R7 and R10 are the same, but R6, R7, R10 and R11 are not hydrogen atom at the same time. In high-temperature solution polymerization of

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poly-α-olefin, in order to improve the polymerization activity, preferably neither R6 nor R11 is hydrogen atom, and more preferably none of R6, R7, R10 and R11 is hydrogen atom. For example, R6 and R11 bonded to the 2-position and 5 7-position of the fluorenyl group are the same hydrocarbon
group having 1 to 20 carbon atoms, and preferably all tert-butyl groups, and R7 and R10 are the same hydrocarbon group having 1 to 20 carbon atoms, and preferably all tert-butyl groups.
10 [0056]
The main chain part (bonding part, Y) connecting the cyclopentadienyl group and the fluorenyl group is a cross-linking section of two covalent bonds comprising one carbon atom or silicon atom, as a structural bridge section
15 imparting steric rigidity to the bridged metallocene compound represented by Formula 1. Cross-linking atom (Y) in the cross-linking section has two aryl groups (R13 and R14) which may be the same or different. Therefore, the cyclopentadienyl group and the fluorenyl group are bonded by the covalent bond
20 cross-linking section containing an aryl group. Examples of the aryl group include a phenyl group, naphthyl group, anthracenyl group, and a substituted aryl group (which is formed by substituting one or more aromatic hydrogen (sp2-type hydrogen) of a phenyl group, naphthyl group or

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anthracenyl group, with substituents). Examples of substituents in the aryl group include a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogen atom etc., and 5 preferably include a phenyl group. In the bridged metallocene compound represented by Formula 1, preferably R13 and R14 are the same in view of easy production. [0057]
In the bridged metallocene compound represented by
10 Formula 1, Q is preferably a halogen atom or hydrocarbon
group having 1 to 10 carbon atoms. The halogen atom includes fluorine, chlorine, bromine or iodine. The hydrocarbon group having 1 to 10 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-
15 dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexyl methyl, cyclohexyl, 1-methyl-1-cyclohexyl etc. Further, when j is an integer of 2 or more, Q may be the same or different.
20 [0058]
Examples of such bridged metallocene compounds (a) include:
ethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, ethylene [η5-(3-tert-

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butyl-5-methyl cyclopentadienyl)] [η5- (3,6-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-tert-butyl-5 5-methyl cyclopentadienyl)] (octamethyl
octahydrodibenzofluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (dibenzofluorenyl)
10 zirconium dichloride, ethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-tert-butyl-
15 5-methyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride;
ethylene [η5-(3-tert-butyl cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)]
20 zirconium dichloride, ethylene [η5-(3-tert-butyl
cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-tert-butyl cyclopentadienyl)] (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl

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cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl cyclopentadienyl)] (dibenzofluorenyl) zirconium dichloride, ethylene [η5-(3-tert-butyl cyclopentadienyl)] (octahydrodibenzofluorenyl) 5 zirconium dichloride, ethylene [η5-(3-tert-butyl
cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride;
10 ethylene [η5-(3-n-butyl cyclopentadienyl)] (η5-
fluorenyl) zirconium dichloride, ethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)]
15 zirconium dichloride, ethylene [η5-(3-n-butyl
cyclopentadienyl)] (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, ethylene [η5-(3-n-butyl cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, ethylene [η5-(3-n-butyl cyclopentadienyl)] (dibenzofluorenyl)
20 zirconium dichloride, ethylene [η5-(3-n-butyl
cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, ethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride, ethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-

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(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride;
diphenylmethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, 5 diphenylmethylene [η5- (3-tert-butyl-5-methyl
cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl-5-
10 methyl cyclopentadienyl)] (octamethyl
octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl-5-methyl
15 cyclopentadienyl)] (dibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl
20 fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-
tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride;
diphenylmethylene [η5-(3-tert-butyl cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-

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tert-butyl cyclopentadienyl)] [η5- (3,6-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-5 tert-butyl cyclopentadienyl)] (octamethyl
octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl cyclopentadienyl)] (dibenzofluorenyl) zirconium
10 dichloride, diphenylmethylene [η5-(3-tert-butyl
cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-
15 tert-butyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride;
diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)]
20 zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-n-butyl

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cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] (dibenzofluorenyl) zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] (octahydrodibenzofluorenyl) 5 zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride, diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride;
10 di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl
cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-
15 butyl-5-methyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl
fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)]
20 (benzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (dibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl)

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39
methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl-5-methyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl 5 fluorenyl)] zirconium dichloride;
di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] (η5-fluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)] zirconium dichloride, di(p-
10 tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] (octamethyl octahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)]
15 (benzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] (dibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl
20 cyclopentadienyl)] [η5-(2,7-diphenyl-3,6-di-tert-butyl
fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-tert-butyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride; and
di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)]

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(η5-fluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(3,6-di-tert-butyl fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl 5 fluorenyl)] zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] (octamethyl
octahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] (benzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl
10 cyclopentadienyl)] (dibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] (octahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] (2,7-diphenyl-3,6-di-tert-butyl fluorenyl) zirconium dichloride, di(p-
15 tolyl) methylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-dimethyl-3,6-di-tert-butyl fluorenyl)] zirconium dichloride. [0059]
Although compounds whose zirconium atoms were substituted with hafnium atoms, or compounds whose chloro
20 ligands were substituted with methyl groups etc. are
exemplified in these compounds, the bridged metallocene compound (a) is not limited to these exemplifications. [0060]
As the organoaluminum oxy-compound used in the catalyst

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41

5

system in the present invention, conventional aluminoxane can be used. For example, linear or ring type aluminoxane represented by the following Formulas 2 to 5 can be used. A small amount of organic aluminum compound may be contained in the organoaluminum oxy-compound. [0061]
R—(-A1— O -)—A1R2

R

(Formula 2)

R ... (Formula 3)
n
■fAl—0-) (-A1—Oi
m

Me

Rx

(Formula 4)

In Formulae 2 to 4, R is independently a hydrocarbon group having 1 to 10 carbon atoms, Rx is independently a 10 hydrocarbon group having 2 to 20 carbon atoms, m and n are
independently an integer of 2 or more, preferably 3 or more, more preferably 10 to 70, and most preferably 10 to 50. [0062]

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d BC pd
R\ T ,R
Al—O—B—O—Ai:
Rd \d
r< R (Formula 5)
In Formula 5, Rc is a hydrocarbon group having 1 to 10 carbon atoms, and Rd is independently a hydrogen atom, halogen atom or hydrocarbon group having 1 to 10 carbon 5 atoms. [0063]
In Formula 2 or Formula 3, R is a methyl group (Me) of the organoaluminum oxy-compound which is conventionally referred to as "methylaluminoxane". 10 [0064]
The methylaluminoxane is easily available and has high polymerization activity, and thus it is commonly used as an activator in the polyolefin polymerization. However, the methylaluminoxane is difficult to dissolve in a saturated 15 hydrocarbon, and thus it has been used as a solution of
aromatic hydrocarbon such as toluene or benzene, which is environmentally undesirable. Therefore, in recent years, a flexible body of methylaluminoxane represented by Formula 4 has been developed and used as an aluminoxane dissolved in 20 the saturated hydrocarbon. The modified methylaluminoxane represented by Formula 4 is prepared by using a trimethyl aluminum and an alkyl aluminum other than the trimethyl

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aluminum as shown in US Patent 4960878 and US Patent 5041584, and for example, is prepared by using trimethyl aluminum and triisobutyl aluminum. The aluminoxane in which Rx is an isobutyl group is commercially available under the trade name 5 of MMAO and TMAO, in the form of a saturated hydrocarbon
solution. (See Tosoh Finechem Corporation, Tosoh Research &
Technology Review, Vol 47, 55 (2003)).
[0065]
As (ii) the compound which reacts with the bridged
10 metallocene compound to form an ion pair (hereinafter, referred to as "ionic compound" as required) which is contained in the present catalyst system, a Lewis acid, ionic compounds, borane, borane compounds and carborane compounds can be used. These are described in patent literatures,
15 Korean Patent No. 10-551147, JP H01-501950 A, JP H03-179005 A, JP H03-179006 A, JP H03-207703 A, JP H03-207704 A, US Patent 5321106 and so on. If needed, heteropoly compounds, and isopoly compound etc. can be used, and the ionic compound disclosed in JP 2004-051676 A can be used. The ionic compound
20 may be used alone or by mixing two or more. In more detail, examples of the Lewis acid include the compound represented by BR3 (R is fluoride, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (methyl group, etc.), substituted or unsubstituted aryl group having 6 to 20 carbon

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atoms (phenyl group, etc.), and also includes for example, trifluoro boron, triphenyl boron, tris(4-fluorophenyl) boron, tris(3,5-difluorophenyl) boron, tris(4-fluorophenyl) boron, tris(pentafluorophenyl) and boron tris(p-tolyl) boron. When 5 the ionic compound is used, its use amount and sludge amount produced are relatively small in comparison with the organoaluminum oxy-compound, and thus it is economically advantageous. In the present invention, it is preferable that the compound represented by the following Formula 6 is used 10 as the ionic compound. [0066]
Rg pe R B—R
R ., ■■■ (Formula 6)
In Formula 6, Re+ is H+, a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a
15 cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and Rf to Ri each is independently an organic group, preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably an aryl group, for example, a penta-fluorophenyl group. Examples of the carbenium cation
20 include a tris(methylphenyl)carbenium cation and a
tris(dimethylphenyl)carbenium cation, and examples of the

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45
ammonium cation include a dimethylanilinium cation. [0067]
Examples of compounds represented by the aforementioned Formula 6 preferably include N,N-dialkyl anilinium salts, and 5 specifically include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis (3,5-ditrifluoro methylphenyl) borate, N,N-diethyl anilinium tetraphenylborate, N,N-diethyl anilinium tetrakis (pentafluorophenyl) borate, N,N-diethyl
10 anilinium tetrakis (3,5-ditrifluoro methylphenyl) borate,
N,N-2,4,6-penta methylanilinium tetraphenylborate, and N,N-2,4,6-penta methylanilinium tetrakis (pentafluorophenyl) borate. [0068]
15 The catalyst system used in the present invention
further includes (c) an organoaluminum compound when it is needed. The organoaluminum compound plays a role of activating the bridged metallocene compound, the organoaluminum oxy-compound, and the ionic compound, etc. As
20 the organoaluminum compound, preferably an organoaluminum represented by the following Formula 7, and alkyl complex compounds of the Group 1 metal and aluminum represented by the following Formula 8 can be used. [0069]

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46
RamAl(ORb)nHpXq … Formula 7 In Formula 7, Ra and Rb each is independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and X is a halogen atom, m is an integer 5 of 0
The lubricating oil composition for internal combustion engines according to the present invention contains a lubricant base oil consisting of the mineral oil (A) and/or 20 synthetic oil (B), and contains the ethylene-α-olefin copolymer (C). [0082]
The lubricating oil composition for internal combustion engines according to the present invention has a kinematic

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viscosity at 100°C of 12.5 mm2/s or more, but less than 26.1 mm2/s. The value of this kinematic viscosity is that when measured according to the method described in JIS K2283. If the kinematic viscosity at 100°C of the lubricating oil 5 composition for internal combustion engines is much more than 26.1 mm2/s, the agitation resistance of the lubricating oil increases in the internal combustion engine parts, and fuel efficiency performance worsens. If the kinematic viscosity at 100°C is much less than 12.5 mm2/s, there is a possibility
10 that metal contact may occur. The kinematic viscosity at
100°C is preferably 13.0 mm2/s or more, but less than 26.1 mm2/s, more preferably 15.0 mm2/s or more, but less than 26.1 mm2/s, and furthermore preferably 16.3 mm2/s or more, but less than 26.1 mm2/s. Within this range, a high fuel efficiency
15 performance is obtainable under a condition of maintaining good shear stability. [0083]
Furthermore, the reduction rate of the kinematic viscosity at 100°C of the lubricating oil composition for
20 internal combustion engines of the present invention, after
the 90-cycle Kurt Orbahn shear test in which a Bosch injector was employed in accordance with ASTM D6278, is usually less than 0.5%. That is, the lubricating oil composition for internal combustion engines of the present invention has a

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53
remarkably high shear stability. When the viscosity reduction rate in this test is less than 0.5%, this lubricating oil composition can be suitably utilized in high-output type engines such as large displacement engines for construction 5 machinery and heavy machinery, or crosshead type diesel
engines oil for ocean vessels, as well as in high-revving engines such as regular- and two-wheeled automobiles for racing, or in such engines of large displacement two-wheeled automobiles such as large-sized two-wheelers.
10 [0084]
In the lubricating oil composition for internal combustion engines of the present invention, there is no particular limitation on the mixing ratio of the lubricant base oil consisting of the mineral oil (A) and/or synthetic
15 oil (B) and the ethylene-α-olefin copolymer (C) if the
required properties in the objective uses are satisfied. However, normally, the mass ratio of the lubricant base oil and the ethylene-α-olefin copolymer (C) (i.e. mass of lubricant base oil / mass of copolymer (C)) is 99/1 to 30/70.
20 [0085]
Moreover, additives such as detergent dispersants, viscosity modifying agents, antioxidants, corrosion preventing agents, anti-wear agents, friction modifying agents, pour point lowering agents, anti-rust agents and

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anti-foamers may be contained in the lubricating oil
composition for internal combustion engines of the present
invention.
[0086]
5 Below are exemplifications of additives which can be
utilized in the lubricating oil composition of the present invention, where these can be used alone, or used in combination of two or more. [0087]
10 Exemplifications of the detergent dispersant include
metal sulfonates, metal phenates, metal phosphonates, and imide succinate. Alkaline metal or alkaline earth metal salicylate-, phenate- or sulfonate- detergents are preferred in the lubricating oil composition of the present invention.
15 Specific exemplifications include sulfonates; phenate; or salicylate of calcium or magnesium; imide succinate; and benzyl amine. The detergent dispersant may be used as required in a range of 0 to 18% by mass with respect to 100% by mass of the lubricating oil composition.
20 [0088]
Detergent dispersants utilized in, in particular, high-output type engines for ocean vessels have a total base value 30 to 350 mg KOH/g as measured by the method described in ISO 3771, and are adjusted so that the detergent dispersants are

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55
in a range of 0.5 to 18% by mass with respect to 100% by mass of the lubricating oil composition, and so that the total base value of the lubricating oil composition is 20 mg KOH/g or more. 5 [0089]
Known viscosity modifying agents such as methacrylate-based copolymers with a molecular weight of less than 50,000, liquid polybutene, and bright stock which is a mineral oil can be used together as the viscosity modifying agent. The
10 viscosity modifying agent is utilized as required in a range of 0 to 50% by mass with respect to 100% by mass of the lubricating oil composition. [0090]
Examples of the antioxidant include phenol-based or
15 amine-based compounds such as 2,6-di-t-butyl-4-methylphenol.
The antioxidant may be used as required in a range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition. [0091]
20 Examples of the corrosion preventing agent include
compounds such as benzotriazole, benzoimidazole, and thiadiazole. The corrosion preventing agent may be used as required in a range of 0 to 3% by mass with respect to 100% by mass of the grease composition.

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56
[0092]
Exemplifications of the anti-wear agent include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, and 5 polytetrafluoroethylene. The anti-wear agent may be used as required in a range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition. [0093]
Exemplifications of the friction modifying agent
10 include amine compounds, imide compound, fatty acid esters,
fatty acid amides, and fatty acid metal salts having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly linear alkyl groups or linear alkenyl groups having 6 to 30 carbon atoms, in a molecule.
15 [0094]
Exemplifications of the amine compound include a linear- or branched-, preferably linear-, aliphatic monoamine, or a linear- or branched-, preferably linear-, aliphatic polyamine having 6 to 30 carbon atoms, or alkylene
20 oxide adducts of these aliphatic amines. Examples of the imide compound include imide succinate with linear- or branched- alkyl group or alkenyl group having 6 to 30 carbon atoms and/or compounds thereof modified by a carboxylic acid, boric acid, phosphoric acid, sulfuric acid etc.

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Exemplifications of the fatty acid ester include esters of a linear- or branched-, preferably linear-, fatty acid having 7 to 31 carbon atoms with an aliphatic monohydric alcohol or aliphatic polyhydric alcohol. Exemplifications of the fatty 5 acid amide include amides of a linear- or branched-,
preferably linear-, fatty acid having 7 to 31 carbon atoms with an aliphatic monoamine or aliphatic polyamine. Examples of fatty acid metal salts include alkaline-earth metal salts (e.g. magnesium salts and calcium salts) and zinc salts of a
10 linear- or branched-, preferably linear-, fatty acid having 7 to 31 carbon atoms. [0095]
The friction modifying agent may be used as required in a range of 0 to 5.0% by mass with respect to 100% by mass of
15 the lubricating oil composition. [0096]
A variety of known pour point lowering agents may be used as the pour point lowering agent. Specifically, high molecular compounds containing an organic acid ester group
20 may be used, and in particular, vinyl polymers containing an organic acid ester group are suitably used. Examples of the vinyl polymer containing an organic acid ester group include (co)polymers of methacrylic acid alkyl, (co)polymers of

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acrylic acid alkyl, (co)polymers of fumaric acid alkyl, (co)polymers of maleic acid alkyl, and alkylated naphthalene. [0097]
Such pour point lowering agents have a melting point of 5 -13°C or lower, preferably -15°C, and furthermore preferably -17°C or lower. The melting point of the pour point lowering agent is measured by means of differential scanning calorimetry (DSC). Specifically, a sample of about 5 mg is packed into an aluminum pan and temperature is raised to
10 200°C, where the temperature is maintained at 200°C for 5
minutes. This is then cooled at 10°C/minute until reaching -40°C, where the temperature is maintained at -40°C for 5 minutes. The temperature is then raised at 10°C/minute during which the melting point is obtained from the heat absorption
15 curve. [0098]
The pour point lowering agent has a polystyrene conversion weight average molecular weight obtainable by gel permeation chromatography in the range of 20,000 to 400,000,
20 preferably 30,000 to 300,000, more preferably 40,000 to 200,000. [0099]
The pour point lowering agent may be used as required in a range of 0 to 2% by mass with respect to 100% by mass of

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the lubricating oil composition. [0100]
Examples of the anti-rust agent include compounds such as amine compounds, carboxylic acid metal salts, polyhydric 5 alcohol esters, phosphorus compounds, and sulfonates. The
anti-rust agent may be used as required in a range of 0 to 3% by mass with respect to 100% by mass of the lubricating oil composition. [0101]
10 Exemplifications of the anti-foamer include silicone-
based compounds such as dimethyl siloxane and silica gel dispersions, and alcohol- or ester-based compounds. The anti-foamer may be used as required in a range of 0 to 0.2% by mass with respect to 100% by mass of the lubricating oil
15 composition. [0102]
In addition to the aforementioned additives, anti-emulsifying agents, coloring agents, oiliness agents (oiliness improving agents) and the like may also be used as
20 required. [0103]
In the lubricating oil for internal combustion engines, the so-called DI package is industrially supplied, where in the DI package, all types of necessary additives are

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formulated for this use, and then concentrated and dissolved in lubricating oil such as mineral oil or synthetic
hydrocarbon oil. Such a DI package can also be applied to the lubricating oil composition of the present invention. 5 [0104]
< Use >
The lubricating oil composition of the present invention can be suitably utilized in internal combustion engine oil with an SAE viscosity standard of 40 or more, and
10 since high fluidity is obtainable at 40°C or lower while maintaining good shear stability, the lubricating oil composition of the present invention can be suitably utilized as fuel efficient engine oil in high-output type engines such as large displacement engines for construction machinery and
15 heavy machinery, or crosshead type diesel engines oil for ocean vessels, as well as in high-revving engines such as regular- and two-wheeled automobiles for racing, or in such engines of large displacement two-wheeled automobiles such as large-sized two-wheelers.
20
Examples
[0105]

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The present invention is further specifically explained based on the below Examples. However, the present invention is not limited to these Examples. [0106] 5 [Evaluation method]
In the below Examples and Comparative Examples etc., the physical properties etc. of the ethylene-α-olefin copolymer and the lubricating oil composition for internal combustion engine oil were measured by the below methods.
10 [0107]
< Ethylene content (mol%) >
Using a Fourier transform infrared spectrometer FT/IR-610 or FT/IR-6100 (made by JASCO), the absorbance ratio of the absorption in the vicinity of 721 cm-1 based on the
15 horizontal vibration of the long chain methylene group, and the absorption in the vicinity of 1155 cm-1 based on the skeletal vibration of propylene (D1155 cm-1 / D721 cm-1) was calculated, and the ethylene content (% by weight) was obtained by the calibration curve created beforehand (created
20 using the ASTM D3900 reference sample). Using the ethylene content (% by weight) thus obtained, the ethylene content (mol%) was obtained according to the following Formula. [0108]

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Ethylene content (mol%)
= [ethylene content (% by weight) / 28]
[ethylene content (% by weight) / 28] + [propylene content (% by weight) / 42]
< B-value >
Employing o-dichloro benzene / benzene-d6 (4/1 5 [vol/vol%]) as a measurement solvent, the 13C-NMR spectrum was measured under the measuring conditions (100 MHz, ECX 400P, made by JEOL Ltd) of temperature of 120°C, spectral width of 250 ppm, pulse repeating time of 5.5 seconds, and a pulse width of 4.7 μsec (45° pulse), or under the measuring 10 conditions (125 MHz, AVANCE III Cryo-500 made by Bruker
Biospin Inc) of temperature of 120°C, spectral width of 250 ppm, pulse repeating time of 5.5 seconds, and a pulse width of 5.0 μsec (45° pulse), and the B-value was calculated based on the following Formula [1].
15 [0109]

In Formula [1], PE indicates the molar fraction contained in the ethylene component, PO indicates the molar fraction contained in the α-olefin component, and POE

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indicates the molar fraction of the ethylene-α-olefin
sequences of all dyad sequences.
[0110]
< Molecular weight distribution >
5 Employing the HLC-8320 GPC (gel permeation
chromatography) device produced by Tosoh Corporation, the molecular weight distribution was measured as below. Four TSK gel Super Multipore HZ-M columns were used as separation columns, the column temperature was 40°C, tetrahydrofuran
10 (made by Wako Pure Chemical Industries) was used as the
mobile phase, with a development rate of 0.35 ml/minute, a sample concentration of 5.5 g/L, a sample injection amount of 20 microliters, and a differential refractometer was used as a detector. PStQuick MP-M; made by Tosoh Corporation) was
15 used as the reference polystyrene. In accordance with
general-purpose calibration procedures, weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and the molecular weight distribution (Mw/Mn) was
20 calculated from those values. [0111]
< Viscosity properties >

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The 100°C kinematic viscosity and the viscosity index was measured and calculated by the method described in JIS K2283. [0112] 5 < CCS viscosity >
The CCS viscosity was measured at -10°C, -15°C, -20°C, -25°C or -30°C by the method described in ASTM D5293. [0113]
< Viscosity reduction rate after the shear test >
10 The Kurt Orbahn 90-cycle shear test was conducted
employing a Bosch injector by the method described in ASTM D6278, and the 100°C kinematic viscosity reduction rate due to shearing, as represented in the below formula (shear test viscosity reduction rate), was evaluated. 15 [0114]
Shear test viscosity reduction rate (%) = (100°C kinematic viscosity before shearing - 100°C kinematic viscosity after shearing) / 100°C kinematic viscosity before shearing x 100 20 < Thermal and oxidation stability >
Regarding thermal and oxidation stability, a test was conducted in accordance with the Oxidation Stability Test of Lubricating Oil for Internal Combustion Engines (ISOT) method

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described in JIS K2514, and the lacquer rating was evaluated 72 hours after the test time. [0115]
[Production of ethylene-α-olefin copolymer (C)]
5 Ethylene-α-olefin copolymers (C) were prepared in
accordance with the Polymerization Examples below. [0116] [Polymerization Example 1]
250 mL of heptane was charged into a glass
10 polymerization vessel with a volume of 1 L sufficiently
substituted with nitrogen, and the temperature in the system was raised to 50°C, and then 25 L/h of ethylene, 75 L/h of propylene, and 100 L/h of hydrogen were continuously supplied into the polymerization vessel, and stirred with a rotation
15 of 600 rpm. Then, 0.2 mmol of triisobutyl aluminum was
charged into the polymerization vessel, and 0.023 mmol of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 0.00230 mmol of diphenylmethylene [η5-(3-n-butyl cyclopentadienyl)] [η5-(2,7-di-tert-butyl fluorenyl)]
20 zirconium dichloride, which were pre-mixed in toluene for 15 minutes or more, were charged into the polymerization vessel to start the polymerization. Ethylene, propylene and hydrogen were then continuously supplied, and polymerization took place at 50°C for 15 minutes. Polymerization was stopped by

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adding a small amount of isobutyl alcohol in the system, and the unreacted monomers were purged. The resulting polymer solution was washed 3 times with 100 mL of a 0.2 mol/L solution of hydrochloric acid, further washed 3 times with 5 100 mL of distilled water, dried with magnesium sulfate, and the solvent was then distilled off under reduced pressure. The resulting polymer was dried overnight at 80°C under reduced pressure to obtain 1.43 g of an ethylene-propylene copolymer. The resulting polymer had an ethylene content of
10 52.4 mol%, an Mw of 13,600, an Mw/Mn of 1.9, a B-value of 1.2, and a 100°C kinematic viscosity of 2,000 mm2/s. [0117] [Polymerization Example 2]
250 mL of heptane was charged into a glass
15 polymerization vessel with a volume of 1 L sufficiently
substituted with nitrogen, and the temperature in the system was raised to 50°C, and then 25 L/h of ethylene, 75 L/h of propylene, and 100 L/h of hydrogen were continuously supplied into the polymerization vessel, and stirred with a rotation
20 of 600 rpm. Then, 0.2 mmol of triisobutyl aluminum was
charged into a polymerization vessel, and 0.688 mmol of MMAO and 0.00230 mmol of dimethylsilyl bis(indenyl) zirconium dichloride, which were pre-mixed in toluene for 15 minutes or more, were charged into a polymerization vessel to start the

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polymerization. Ethylene, propylene and hydrogen were then continuously supplied, and polymerization took place at 50°C for 15 minutes. Polymerization was stopped by adding a small amount of isobutyl alcohol in the system, and the unreacted 5 monomers were purged. The resulting polymer solution was washed 3 times with 100 mL of a 0.2 mol/L solution of hydrochloric acid, further washed 3 times with 100 mL of distilled water, dried with magnesium sulfate, and the solvent was then distilled off under reduced pressure. The
10 resulting polymer was dried overnight at 80°C under reduced
pressure to obtain 1.43 g of an ethylene-propylene copolymer. The resulting polymer had an ethylene content of 52.1 mol%, an Mw of 13,800, an Mw/Mn of 2.0, a B-value of 1.2, and a 100°C kinematic viscosity of 2,000 mm2/s.
15 [0118]
The copolymer obtained by Polymerization Example 1, and the copolymer obtained by Polymerization Example 2, are respectively described below as Polymer 1 and Polymer 2. [0119]
20 [Preparation of lubricating oil composition for internal combustion engines]
The components used other than the ethylene-α-olefin copolymer (C) in the preparation of the below lubricating oil compositions are as follows.

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Lubricant base oil; The below lubricant base oils were utilized as the Mineral oil (A).
Mineral oil - A: API Group I mineral oil with a 100°C kinematic viscosity of 6.8 mm2/s, a viscosity index of 97, 5 and a pour point -12.5°C (Super Oil N-46, made by JX Nippon Oil & Energy Corporation)
Mineral oil - B: API Group I mineral oil with a 100°C kinematic viscosity of 8.8 mm2/s, a viscosity index of 101, and a pour point -12.5°C (Super Oil N-68, made by JX Nippon 10 Oil & Energy Corporation)
Mineral oil - C: API Group I mineral oil with a 100°C
kinematic viscosity of 5.3 mm2/s, a viscosity index of 106,
and a pour point -12.5°C (Super Oil N-32, made by JX Nippon
Oil & Energy Corporation)
15 Mineral oil - D: API Group III mineral oil with a 100°C
kinematic viscosity of 4.2 mm2/s, a viscosity index of 122, and a pour point of -15°C (Yubase-4, made by SK Lubricants)
Mineral oil - E: API Group III mineral oil with a 100°C kinematic viscosity of 6.5 mm2/s, a viscosity index of 131, 20 and a pour point -12°C (Yubase-6, made by SK Lubricants) Synthetic oil (B); The below lubricant base oils were utilized as the Synthetic Oil (B).
Synthetic oil - A: a synthetic oil poly-α-olefin with a 100°C kinematic viscosity of 4.0 mm2/s, a viscosity index of

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123, and pour point of -60°C or lower (NEXBASE 2004, made by Neste)
Synthetic oil - B: a synthetic oil poly-α-olefin with a 100°C kinematic viscosity of 5.8 mm2/s, a viscosity index of 5 138, and a pour point of -60°C or lower (NEXBASE 2006, made by Neste)
Synthetic oil - C: diisodecyl adipate, a fatty acid ester with a 100°C kinematic a viscosity of 3.7 mm2/s, viscosity index of 156, and a pour point of -60°C or lower 10 (made by Daihachi Chemical Industry Co. Ltd.) DI package (DI);
P-5202 made by Infineum Pour point lowering agent (PPD);
IRGAFLO 720P made by BASF 15 Bright stock;
API Group I mineral oil with a 100°C kinematic viscosity of 29.9 mm2/s, a viscosity index of 97, and a pour point -10.0°C (Bright Stock N460, made by JX Nippon Oil & Energy Corporation) 20 < Lubricating oil composition for internal combustion engines > [Example 1]
Mineral oil-A and Mineral oil–B, which are the Mineral oil (A), was used as the lubricant base oil, and the

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copolymer obtained in Polymerization Example 1 (Polymer 1) was used as the ethylene-α-olefin copolymer (C). These were mixed together in the usual manner with the DI package (DI) and the pour point lowering agent (PPD), thereby preparing a 5 lubricating oil composition for internal combustion engine oil. The addition amounts of the respective components and the physical properties etc. of the resulting lubricating oil compositions are as shown in Table 3. [0120]
10 [Examples 2 to 6, Comparative Examples 1 to 5]
Except for changing the types of components and addition amounts to those as described in Table 3, the lubricating oil compositions were prepared in the same way as in Example 1. The physical properties of the resulting
15 lubricating oil compositions are as shown in Table 3.

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Table 3

Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Comp. ex. 1 Comp. ex. 2 Comp. ex. 3 Comp. ex. 4 Comp. ex. 5
Polymer 1 % by mass 4.0 5.0 9.0 8.0 12.0 14.0
Polymer 2 % by mass 4.0 5.0 9.0
Bright stock % by mass 26.5 44.2
Mineral oil – A % by mass 54.9 54.3 51.7 54.9 54.3 51.7 40.3 28.8
Mineral oil – B % by mass 29.6 29.2 27.8 29.6 29.2 27.8 21.7 15.5
Mineral oil – C % by mass 80.5 76.5 74.5
DI % by mass 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0
PPD % by mass 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
100°C
kinematic
viscosity mm2/s 16.2 17.7 24.6 15.1 21.3 25.5 16.3 17.5 24.4 15.4 19.0
Viscosity index - 121 124 134 143 152 157 122 122 134 105 103
-10°C CCS viscosity mPa･s 4,500 5,000 7,600 2,600 3,900 4,700 6,200 11,000
-15°C CCS viscosity mPa･s 8,600 9,300 14,000 4,200 6,500 8,200 13,000 23,000
ISOT Varnish rating Adhered
substance
(thin) Adhered
substance
(thin) Adhered substance (medium) Adhered substance (medium) Adhered substance (medium) Adhered substance (medium) Adhered
substance
(thick) Adhered
substance
(thick) Adhered
substance
(thick) Adhered
substance
(thick) Adhered
substance
(thick)

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[Example 7]
Mineral oil-D and Mineral oil–E, which are the Mineral oil (A), were used as the lubricant base oil, and polymer 1 was used as the ethylene-α-olefin copolymer (C). These were 5 mixed together in the usual manner with the DI package (DI)
and the pour point lowering agent (PPD), thereby preparing a lubricating oil composition for internal combustion engine oil. The addition amounts of the respective components and the physical properties etc. of the resulting lubricating oil
10 compositions are as shown in Table 4. [0122] [Example 8 to 15, Comparative Examples 6 to 8]
Except for changing the types of components and addition amounts to those as described in Table 4, the
15 lubricating oil compositions for internal combustion engine oil were prepared in the same way as in Example 7. The physical properties etc. of the resulting lubricating oil compositions are as shown in Table 4.

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73 [0123]
Table 4

Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Comp. ex. 6 Comp. ex. 7 Comp. ex. 8
Polymer 1 % by mass 8.0 11 .0 14.5 10.0 13.0 17.0 8.0 11 .0 15.0
Polymer 2 % by mass 8.0 10.0 8.0
Mineral oil - D % by mass 48.3 46.5 44.4 48.3
Mineral oil - E % by mass 32.2 31.0 29.6 32.2
Synthetic oil - A % by mass 59.0 56.0 52.0 59.0
Synthetic oil - B % by mass 61.0 58.0 54.0 61.0
Synthetic oil - C % by mass 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0
DI % by mass 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0 11 .0
PPD % by mass 0.5 0.5 0.5 0.5
100°C kinematic viscosity mm2/s 13.5 17.6 24.5 13.0 17.0 23.8 13.7 17.6 24.4 13.5 13.1 13.8
Viscosity index - 161 165 168 172 178 189 164 169 173 160 172 165
-15°C CCS viscosity mPa･s 4,920 3,920
-20°C CCS viscosity mPa･s 3,750 5,990 5,920 4,830
-25°C CCS viscosity mPa･s 6,160 5,470
-30°C CCS viscosity mPa･s 6,430
Viscosity reduction rate after shear test % < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5
ISOT Varnish rating Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thin) Adhered
substance
(thick) Adhered
substance
(thick) Adhered
substance
(thick)

WE CLAIMS

A lubricating oil composition for internal combustion
engines, comprising a lubricant base oil, and a liquid random 5 copolymer (C) of ethylene and α-olefin, the liquid random
copolymer (C) being prepared by the below method (α), the
lubricating oil composition having a kinematic viscosity at
100°C of 12.5 mm2/s or more, but less than 26.1 mm2/s,
wherein the lubricant base oil consists of a mineral 10 oil (A) having the properties of the below (A1) to (A3),
and/or a synthetic oil (B) having the properties of the below
(B1) to (B3).
(A1) The mineral oil has a kinematic viscosity at 100°C of 2
to 10 mm2/s. 15 (A2) The mineral oil has a viscosity index of 95 or more.
(A3) The mineral oil has a pour point of -10°C or lower.
(B1) The synthetic oil has a kinematic viscosity at 100°C of
1 to 10 mm2/s.
(B2) The synthetic oil has a viscosity index of 120 or more. 20 (B3) The synthetic oil has a pour point of -30°C or lower.
(Method (α))
A method (α) for preparing a liquid random copolymer of
ethylene and α-olefin, comprising a step of carrying out
solution polymerization of ethylene and α-olefin having 3 to

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20 carbon atoms, under a catalyst system comprising
(a) a bridged metallocene compound represented by the
following Formula 1, and
(b) at least one compound selected from a group consisting of
5 (i) an organoaluminum oxy-compound, and
(ii) a compound which reacts with the bridged metallocene compound to form an ion pair.

(Formula 1)
[In Formula 1, R1, R2, R3, R4, R5, R8, R9 and R12 are 10 respectively and independently hydrogen atom, hydrocarbon
group or silicon-containing hydrocarbon group, and adjoining groups are optionally connected to each other to form a ring structure,
R6 and R11, being the same, are hydrogen atom,

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hydrocarbon group or silicon-containing hydrocarbon group,
R7 and R10, being the same, are hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group,
R6 and R7 are optionally connected to hydrocarbon having 5 2 to 3 carbon atoms to form a ring structure,
R11 and R10 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,
R6, R7, R10 and R11 are not hydrogen atom at the same
time;
10 Y is a carbon atom or silicon atom;
R13 and R14 are independently aryl group;
M is Ti, Zr or Hf;
Q is independently halogen, hydrocarbon group, an anionic ligand or a neutral ligand which can be coordinated 15 to a lone pair of electrons; and
j is an integer of 1 to 4.]
2. The lubricating oil composition for internal combustion engines according to Claim 1, wherein in the metallocene 20 compound represented by the above Formula 1, at least one among substituents (R1, R2, R3 and R4) bonded to a
cyclopentadienyl group, is a hydrocarbon group having 4 or more carbon atoms.

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3. The lubricating oil composition for internal combustion engines according to Claim 1 or 2, wherein R6 and R11, being the same, are hydrocarbon groups having 1 to 20 carbon atoms.
5 4. The lubricating oil composition for internal combustion engines according to any one of Claims 1 to 3, wherein in the metallocene compound represented by the above Formula 1, substituent (R2 or R3) bonded to the 3-position of the cyclopentadienyl group is a hydrocarbon group. 10
5. The lubricating oil composition for internal combustion
engines according to Claim 4, wherein in the metallocene
compound represented by the above Formula 1, the hydrocarbon
group (R2 or R3) bonded to the 3-position of the
15 cyclopentadienyl group is an n-butyl group.
6. The lubricating oil composition for internal combustion
engines according to any one of Claims 1 to 5, wherein in the
metallocene compound represented by the above Formula 1,
20 substituents (R6 and R11) bonded to the 2-position and 7-position of the fluorenyl group are all tert-butyl groups.
7. The lubricating oil composition for internal combustion
engines according to any one of Claims 1 to 6, wherein the

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compound which reacts with the bridged metallocene compound to form an ion pair is a compound represented by the following Formula 6.
Rg pe R B—R
R ., ■■■ (Formula 6)
5 [In Formula 6, Re+ is H+, a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and Rf to Ri each is independently a hydrocarbon group having 1 to 20 carbon atoms.] 10
8. The lubricating oil composition for internal combustion engines according to Claim 7, wherein the ammonium cation is a dimethylanilinium cation.
15 9. The lubricating oil composition for internal combustion engines according to Claim 7 or 8, wherein the catalyst system further comprises an organoaluminum compound selected from a group consisting of trimethyl aluminum and triisobutyl aluminum.
20

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10. The lubricating oil composition for internal combustion engines according to any of Claims 1 to 9, wherein the α-olefin of the liquid random copolymer (C) is propylene.
5 11. A lubricating oil composition for internal combustion engines, comprising a lubricant base oil, and a liquid random copolymer of ethylene and α-olefin, the liquid random copolymer having the properties of the below (C1) to (C5), the lubricating oil composition having a kinematic viscosity
10 at 100°C of 12.5 mm2/s or more, but less than 26.1 mm2/s,
wherein the lubricant base oil consists of a mineral oil (A) having the properties of the below (A1) to (A3), and/or a synthetic oil (B) having the properties of the below (B1) to (B3).
15 (A1) The mineral oil has a kinematic viscosity at 100°C of 2 to 10 mm2/s.
(A2) The mineral oil has a viscosity index of 95 or more. (A3) The mineral oil has a pour point of -10°C or lower. (B1) The synthetic oil has a kinematic viscosity at 100°C of
20 1 to 10 mm2/s.
(B2) The synthetic oil has a viscosity index of 120 or more. (B3) The synthetic oil has a pour point of -30°C or lower. (C1) The liquid random copolymer comprises 40 to 60 mol% of ethylene units and 60 to 40 mol% of α-olefin units having 3

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to 20 carbon atoms.
(C2) The liquid random copolymer has a number average molecular weight (Mn) of 500 to 10,000 and a molecular weight distribution (Mw/Mn, Mw is the weight average molecular 5 weight) of 3 or less, as measured by Gel Permeation Chromatography (GPC).
(C3) The liquid random copolymer has a kinematic viscosity at 100°C of 30 to 5,000 mm2/s.
(C4) The liquid random copolymer has a pour point of 30 to -10 45°C.
(C5) The liquid random copolymer has a Bromine Number of 0.1 g / 100 g or less.
12. The lubricating oil composition for internal combustion
15 engines according to any of Claims 1 to 11, wherein the
synthetic oil (B) contains an ester, and a synthetic oil other than ester.
13. The lubricating oil composition for internal combustion
20 engines according to any of Claims 1 to 12, having a total
base value of at least 20 mg-KOH/g.
14. A diesel engine oil, consisting of the lubricating oil
composition for internal combustion engines according to any

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of Claims 1 to 13.
15. A method for producing a lubricating oil composition
for internal combustion engines, comprising the steps of:
5 preparing a liquid random copolymer (C) of ethylene and
α-olefin by the following method (α); and
preparing a lubricating oil composition for internal
combustion engines by mixing a lubricant base oil and the
liquid random copolymer (C), the composition having a 10 kinematic viscosity at 100°C of 12.5 mm2/s or more, but less
than 26.1 mm2/s,
wherein the lubricant base oil consists of a mineral
oil (A) having the properties of the below (A1) to (A3),
and/or a synthetic oil (B) having the properties of the below 15 (B1) to (B3).
(A1) The mineral oil has a kinematic viscosity at 100°C of 2
to 10 mm2/s.
(A2) The mineral oil has a viscosity index of 95 or more.
(A3) The mineral oil has a pour point of -10°C or lower. 20 (B1) The synthetic oil has a kinematic viscosity at 100°C of
1 to 10 mm2/s.
(B2) The synthetic oil has a viscosity index of 120 or more.
(B3) The synthetic oil has a pour point of -30°C or lower.
(Method (α))

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A method (α) for preparing a liquid random copolymer of ethylene and α-olefin, comprising a step of carrying out solution polymerization of ethylene and α-olefin having 3 to 20 carbon atoms, under a catalyst system comprising 5 (a) a bridged metallocene compound represented by the following Formula 1, and
(b) at least one compound selected from a group consisting of (i) an organoaluminum oxy-compound, and (ii) a compound which reacts with the bridged 10 metallocene compound to form an ion pair.

Ry RB ■■• (Formula 1)
[In Formula 1, R1, R2, R3, R4, R5, R8, R9 and R12 are respectively and independently hydrogen atom, hydrocarbon group or silicon-containing hydrocarbon group, and adjoining

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groups are optionally connected to each other to form a ring structure,
R6 and R11, being the same, are hydrogen atom,
hydrocarbon group or silicon-containing hydrocarbon group,
5 R7 and R10, being the same, are hydrogen atom,
hydrocarbon group or silicon-containing hydrocarbon group,
R6 and R7 are optionally connected to hydrocarbon having 2 to 3 carbon atoms to form a ring structure,
R11 and R10 are optionally connected to hydrocarbon 10 having 2 to 3 carbon atoms to form a ring structure,
R6, R7, R10 and R11 are not hydrogen atom at the same time;
Y is a carbon atom or silicon atom;
R13 and R14 are independently aryl group;
15 M is Ti, Zr or Hf;
Q is independently halogen, hydrocarbon group, an anionic ligand or a neutral ligand which can be coordinated to a lone pair of electrons; and
j is an integer of 1 to 4.] 20