Technical Field
[0001] The present invention relates to a lubricating oil composition.
Background Art
[0002] In the related art, lubricating oils are used for internal combustion engines, transmissions,
and other machine apparatuses to smooth their action. Particularly in lubricating
oil for internal combustion engines (engine oil), high performance is required with
higher performance of the internal combustion engines, higher outputs, severer operation
conditions, and the like. Accordingly, to meet such required performances, various
additives such as anti-wear agents, metallic detergents, ash-free dispersants, and
antioxidants are blended with the conventional engine oil (for example, see Patent
Literatures 1 to 3 below). Moreover, the fuel efficiency required for the lubricating
oil is increasing recently, and application of base oil having high viscosity index
and application of a variety of friction modifiers are examined (for example, see
Patent Literature 4 below).
Citation List
Patent Literature
Summary of Invention
Technical Problem
[0005] However, it cannot be said that the conventional lubricating oils are sufficient
in fuel efficiency.
[0006] For example, as a standard method for fuel efficiency, a reduction in the kinematic
viscosity of the lubricating oil and an increase in the viscosity index (multi-grading
by a combination of low viscosity base oils with viscosity index improvers), and blending
of friction reducing agents are known. In the case of a reduction in viscosity, the
lubrication performance is reduced under severe lubrication conditions (under high
temperature high shear conditions) due to a reduction of the viscosity of the lubricating
oil or the base oil that forms the lubricating oil, occurrence of failures such as
wear, burning, and fatigue breaking is concerned. Moreover, for blending of friction
reducing agents, ash-free friction modifiers and molybdenum friction modifiers are
known, but there is demand for an oil with fuel efficiency superior to that of standard
oils having theses friction reducing agents.
[0007] To prevent deficits in the reduction in viscosity and give fuel efficiency while
maintaining durability, it is effective to increase an HTHS viscosity at 150°C ("HTHS
viscosity" is also referred to as "high temperature high shear viscosity") while reducing
a kinematic viscosity at 40°C, a kinematic viscosity at 100°C, and an HTHS viscosity
at 100°C; however, it is very difficult for the conventional lubricating oil to satisfy
these requirements all.
[0008] To maintain durability while further improving fuel efficiency, it is important to
reduce a reduction in viscosity by usage while reducing the kinematic viscosity of
a new oil and the HTHS viscosity at 100°C. It is also important to reduce the coefficient
of friction in a boundary lubrication region while reducing kinematic viscosity as
much as possible.
[0009] The present invention has been made in consideration of such circumstances, and an
object of the present invention is to provide a lubricating oil composition excellent
in durability and fuel efficiency that can reduce a kinematic viscosity at 40°C and
a kinematic viscosity at 100°C from the beginning of usage after usage for a long
time, and can suppress a reduction in viscosity after shear.
Solution to Problem
[0010] To solve the problems above, the present invention provides a lubricating oil composition
including a lubricating base oil having a kinematic viscosity at 100°C of 1 to 10
mm
2/s, and 0.1 to 50 % by mass of a branched poly(meth)acrylate viscosity index improver
(A) containing one or two or more structural units represented by the following formula
(1) in the proportion of 30 to 90 mol% and having a branching degree of 0.1 to 8.0:

wherein R
1 represents hydrogen or a methyl group, and R
2 represents a linear or branched hydrocarbon group having a carbon number of 6 or
less.
[0011] The viscosity index improver (A) is a viscosity index improver having a PSSI of 5
or less and a ratio of the molecular weight to the PSSI (Mw/PSSI) of 2 × 10
4 or more.
[0012] It is preferable that the lubricating oil composition further comprises a friction
modifier (B).
[0013] Here, the term "PSSI" in the present invention means a permanent shear stability
index of a polymer (Permanent Shear Stability Index) in accordance with ASTM D 6022-01
(Standard Practice for Calculation of Permanent Shear Stability Index) calculated
based on the data measured in accordance with ASTM D 6278-02 (Test Method for Shear
Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus).
Advantageous Effects of Invention
[0014] As above, according to the present invention, a lubricating oil composition excellent
in durability and fuel efficiency that can sufficiently reduce the kinematic viscosity
at 40°C and the kinematic viscosity at 100°C from the beginning of usage after usage
for a long time while maintaining the HTHS viscosity at 150°C, and can sufficiently
suppress a reduction in viscosity after shear can be provided.
[0015] Moreover, the lubricating oil composition according to the present invention can
be suitably used not only for gasoline engines, diesel engines, gas engines, and the
like for bicycles, automobiles, power generation, cogeneration, and the like but also
for a variety of engines using fuels having a sulfur content of 50 mass ppm or less.
The lubricating oil composition according to the present invention is also useful
for a variety of engines for ships and outboard motors.
Description of Embodiments
[0016] Hereinafter, suitable Embodiment of the present invention will be described in detail.
[0017] The lubricating oil composition according to the present embodiment contains a lubricating
base oil having a kinematic viscosity at 100°C of 1 to 10 mm
2/s, and a branched poly(meth)acrylate viscosity index improver (A) containing one
or two or more structural units represented by the following formula (1) in the proportion
of 30 to 90 mol% and having a branching degree is 0.1 to 8.0:

wherein R
1 represents hydrogen or a methyl group, and R
2 represents a linear or branched hydrocarbon group having a carbon number of 6 or
less.
[0018] In the lubricating oil composition according to the present embodiment, a lubricating
base oil having a kinematic viscosity at 100°C of 1 to 10 mm
2/s (hereinafter referred to as a "lubricating base oil according to the present embodiment")
is used.
[0019] Examples of the lubricating base oil according to the present embodiment include
those having a kinematic viscosity at 100°C of 1 to 5 mm
2/s among paraffin mineral oils, normal paraffin base oils, and isoparaffin base oils
obtained by refining a lubricating oil fraction obtained by normal pressure distillation
and/or reduced pressure distillation of a crude oil using one or two or more refining
treatments selected from solvent deasphalting, solvent extraction, hydrocracking,
solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment,
and the like.
[0020] Preferable examples of the lubricating base oil according to the present embodiment
can include base oils obtained by using the base oils (1) to (8) shown below as the
raw material, and refining the raw material oil and/or a lubricating oil fraction
recovered from the raw material oil by a predetermined refining method to recover
a lubricating oil fraction:
- (1) Distilled oil obtained by normal pressure distillation of a paraffinic crude oil
and/or a mixed-base crude oil,
- (2) Distilled oil obtained by reduced pressure distillation of a paraffinic crude
oil and/or a normal pressure distillation residue oil of a mixed-base crude oil (WVGO),
- (3) Waxes obtained by a lubricating oil dewaxing step (such as slack wax) and/or synthetic
waxes obtained by a gas-to-liquid (GTL) process or the like (such as Fischer-Tropsch
wax and GTL wax),
- (4) One or two or more mixed oils selected from the base oils (1) to (3) and/or a
mild hydrocracked oil of the mixed oil,
- (5) Two or more mixed oils selected from the base oils (1) to (4),
- (6) Deasphalted oil (DAO) of the base oil (1), (2), (3), (4) or (5),
- (7) Mild hydrocracked oil (MHC) of the base oil (6) (MHC), and
- (8) Mixed oil of two or more selected from the base oils (1) to (7).
[0021] For the predetermined refining method, hydrorefining such as hydrocracking and hydrofinishing;
solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing
and catalytic dewaxing; white clay refining with acid clay or activated clay; and
chemical (acid or alkali) washing such as sulfuric acid washing and sodium hydroxide
washing are preferable. In the present embodiment, among these refining methods, one
method may be used alone, or two or more may be used in combination. If two or more
refining methods are combined, the order is not particularly limited, and can be properly
selected.
[0022] Furthermore, for the lubricating base oil according to the present embodiment, a
base oil selected from the base oils (1) to (8) or the following base oil (9) or (10)
obtained by performing a predetermined treatment on the lubricating oil fraction recovered
from the base oil is particularly preferable:
(9) Hydrocracking base oils obtained by hydrocracking the base oil selected from the
base oils (1) to (8) or the lubricating oil fraction recovered from the base oil,
and performing a dewaxing treatment such as solvent dewaxing and catalytic dewaxing
on the product or the lubricating oil fraction recovered from the product by distillation
or the like, or performing distillation after the dewaxing treatment, and
(10) Hydrogenation isomerized base oils obtained by hydrogenation isomerizing the
base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered
from the base oil, and performing a dewaxing treatment such as solvent dewaxing and
catalytic dewaxing on the product or the lubricating oil fraction recovered from the
product by distillation or the like, or performing distillation after the dewaxing
treatment.
[0023] In production of the lubricating base oil (9) or (10), a solvent refining treatment
and/or a hydrofinishing step may be included as preferably steps when necessary.
[0024] The catalyst used in the hydrocracking and hydrogenation isomerization is not particularly
limited, and hydrocracking catalysts in which a carrier is a composite oxide having
cracking activity (such as silica alumina, alumina boria, and silica zirconia) or
one or more of the composite oxides in combination bounded by a binder, and a metal
having a hydrogenation activity (such as one or more metals in Groups VIa and VIII
in the periodic table) is carried to the carrier; or hydrogenation isomerization catalysts
in which a metal containing at least one metal among metals in Group VIII and having
a hydrogenation activity is carried to a carrier containing zeolite (such as ZSM-5,
zeolite beta, and SAPO-11) are preferably used. The hydrocracking catalyst and the
hydrogenation isomerization catalyst may be used in combination by stacking or mixing.
[0025] The reaction conditions in hydrocracking and hydrogenation isomerization are not
particularly limited, and a hydrogen partial pressure of 0.1 to 20 MPa, an average
reaction temperature of 150 to 450°C, LHSV of 0.1 to 3.0 hr
-1, and the ratio of hydrogen/oil of 50 to 20000 scf/b are preferred.
[0026] The kinematic viscosity at 100°C of the lubricating base oil according to the present
embodiment needs to be 10 mm
2/s or less, preferably 4.5 mm
2/s or less, more preferably 4 mm
2/s or less, still more preferably 3.8 mm
2/s or less, particularly preferably 3.7 mm
2/s or less, and most preferably 3.6 mm
2/s or less. The kinematic viscosity at 100°C needs to be 1 mm
2/s or more. It is preferable that the kinematic viscosity at 100°C be 1.5 mm
2/s or more. The kinematic viscosity at 100°C is more preferably 2 mm
2/s or more, still more preferably 2.5 mm2/s or more, and particularly preferably 3
mm
2/s or more. The kinematic viscosity at 100°C here designates the kinematic viscosity
at 100°C specified in ASTM D-445. In the case where the kinematic viscosity at 100°C
of the lubricating base oil exceeds 10 mm
2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency
may not be obtained. At a kinematic viscosity of 1 mm
2/s or less, formation of an oil film in a lubrication place is insufficient; for this
reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition
may be increased.
[0027] The kinematic viscosity at 40°C of the lubricating base oil according to the present
embodiment is preferably 40 mm
2/s or less, more preferably 30 mm
2/s or less, still more preferably 25 mm
2/s or less, particularly preferably 20 mm
2/s or less, and most preferably 17 mm
2/s or less. The kinematic viscosity at 40°C is preferably 6.0 mm
2/s or more, more preferably 8.0 mm
2/s or more, still more preferably 10 mm
2/s or more, particularly preferably 12 mm
2/s or more, and most preferably 14 mm
2/s or more. In the case where the kinematic viscosity at 40°C of the lubricating base
oil exceeds 40 mm
2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency
may not be obtained. At a kinematic viscosity of 6.0 mm
2/s or less, formation of an oil film in a lubrication place is insufficient; for this
reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition
may be increased.
[0028] It is preferable that the viscosity index of the lubricating base oil according to
the present embodiment be 100 or more. The viscosity index is more preferably 105
or more, still more preferably 110 or more, particularly preferably 115 or more, and
most preferably 120 or more. If the viscosity index is less than 100, not only viscosity-temperature
properties, heat and oxidation stability, and anti-volatilization are reduced, but
also the coefficient of friction tends to be increased; and resistance against wear
tends to be reduced.
[0029] The viscosity index in the present invention means the viscosity index measured according
to JIS K 2283-1993.
[0030] It is preferable that the lubricating base oil in the lubricating oil composition
according to the present embodiment be a mixture of a first lubricating base oil component
having a kinematic viscosity at 100°C of 3.5 mm
2/s or more and having a viscosity index of 120 or more and a second lubricating base
oil component having a kinematic viscosity at 100°C of less than 3.5 mm
2/s. By using the mixture of the first lubricating base oil component and the second
lubricating base oil component, high viscosity temperature properties can be given
to improve fuel efficiency more significantly.
[0031] The density (ρ
15) at 15°C of the first lubricating base oil component used in the lubricating oil
composition according to the present embodiment is preferably 0.860 or less, more
preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably
0.822 or less.
[0032] The density at 15°C in the present invention means a density measured at 15°C according
to JIS K 2249-1995.
[0033] The pour point of the first lubricating base oil component used in the lubricating
oil composition according to the present embodiment is preferably -10°C or less, more
preferably -12.5°C or less, still more preferably -15°C or less, and particularly
preferably -20°C or less. If the pour point exceeds the upper limit value, the fluidity
at a low temperature of the entire lubricating oil using the lubricating base oil
tends to be reduced. The pour point in the present invention means the pour point
measured according to JIS K 2269-1987.
[0034] It is preferable that the kinematic viscosity at 100°C of the first lubricating base
oil component used in the lubricating oil composition according to the present embodiment
be 5 mm
2/s or less. The kinematic viscosity is more preferably 4.5 mm
2/s or less, still more preferably 4.0 mm
2/s or less, and particularly preferably 3.9 mm
2/s or less. It is preferable that the kinematic viscosity at 100°C be 3.5 mm
2/s or more. The kinematic viscosity is more preferably 3.6 mm
2/s or more, still more preferably 3.7 mm
2/s or more, and particularly preferably 3.8 mm
2/s or more. If the kinematic viscosity at 100°C exceeds 5 mm
2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency
may not be obtained. At a kinematic viscosity less than 3.5 mm
2/s, formation of an oil film in a lubrication place is insufficient; for this reason,
lubrication is inferior, and the evaporation loss of the lubricating oil composition
may be increased.
[0035] The kinematic viscosity at 40°C of the first lubricating base oil component used
in the lubricating oil composition according to the present embodiment is preferably
40 mm
2/s or less, more preferably 30 mm
2/s or less, still more preferably 25 mm
2/s or less, particularly preferably 20 mm
2/s or less, and most preferably 17 mm
2/s or less. The kinematic viscosity at 40°C is preferably 6.0 mm
2/s or more, more preferably 8.0 mm
2/s or more, still more preferably 10 mm
2/s or more, particularly preferably 12 mm
2/s or more, and most preferably 14 mm
2/s or more. In the case where the kinematic viscosity at 40°C exceeds 40 mm
2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency
may not be obtained. At a kinematic viscosity of 6.0 mm
2/s or less, formation of an oil film in a lubrication place is insufficient; for this
reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition
may be increased.
[0036] It is preferable that the viscosity index of the first lubricating base oil component
used in the lubricating oil composition according to the present embodiment be 100
or more. The viscosity index is more preferably 110 or more, still more preferably
120 or more, particularly preferably 130 or more, and most preferably 140 or more.
The viscosity index is preferably 170 or less, more preferably 160 or less, still
more preferably 155 or less, and particularly preferably 150 or less. If the viscosity
index is less than 100, not only viscosity-temperature properties, heat and oxidation
stability, and anti-volatilization are reduced, but also the coefficient of friction
tends to be increased; and resistance against wear tends to be reduced. If the viscosity
index exceeds 170, low temperature viscosity tends to be increased to reduce the fuel
efficiency at low oil temperatures. Moreover, startability tends to be reduced.
[0037] The density (ρ
15) at 15°C of the second lubricating base oil component used in the lubricating oil
composition according to the present embodiment is preferably 0.860 or less, more
preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably
0.835 or less.
[0038] The pour point of the second lubricating base oil component used in the lubricating
oil composition according to the present embodiment is preferably -10°C or less, more
preferably -12.5°C or less, still more preferably -15°C or less, and particularly
preferably -20°C or less. If the pour point exceeds the upper limit value, the fluidity
at a low temperature of the entire lubricating oil using the lubricating base oil
tends to be reduced.
[0039] It is preferable that the kinematic viscosity at 100°C of the second lubricating
base oil component used in the lubricating oil composition according to the present
embodiment be less than 3.5 mm
2/s. The kinematic viscosity is more preferably 3.4 mm
2/s or less, and still more preferably 3.3 mm
2/s or less. It is preferable that the kinematic viscosity at 100°C be 2 mm
2/s or more, and the kinematic viscosity is more preferably 2.5 mm
2/s or more, and still more preferably 3.0 mm
2/s or more. If the kinematic viscosity at 100°C exceeds 3.5 mm
2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency
may not be obtained. At a kinematic viscosity less than 2 mm
2/s, formation of an oil film in a lubrication place is insufficient; for this reason,
lubrication is inferior, and the evaporation loss of the lubricating oil composition
may be increased.
[0040] The kinematic viscosity at 40°C of the second lubricating base oil component used
in the lubricating oil composition according to the present embodiment is preferably
20 mm
2/s or less, more preferably 18 mm
2/s or less, still more preferably 16 mm
2/s or less, and particularly preferably 14 mm
2/s or less. The kinematic viscosity at 40°C is preferably 6.0 mm
2/s or more, more preferably 8.0 mm
2/s or more, still more preferably 10 mm
2/s or more, particularly preferably 12 mm
2/s or more, and most preferably 13 mm
2/s or more. If the kinematic viscosity at 40°C exceeds 20 mm
2/s, low temperature viscosity properties may be reduced, and sufficient fuel efficiency
may not be obtained. At a kinematic viscosity of 6.0 mm
2/s or less, formation of an oil film in a lubrication place is insufficient; for this
reason, lubrication is inferior, and the evaporation loss of the lubricating oil composition
may be increased.
[0041] It is preferable that the viscosity index of the second lubricating base oil component
used in the lubricating oil composition according to the present embodiment be 100
or more. The viscosity index is more preferably 105 or more, and still more preferably
110 or more. The viscosity index is preferably 160 or less, more preferably 150 or
less, still more preferably 140 or less, and particularly preferably 135 or less.
If the viscosity index is less than 100, not only viscosity-temperature properties,
heat and oxidation stability, and anti-volatilization are reduced, but also the coefficient
of friction tends to be increased. Moreover, resistance against wear tends to be reduced.
If the viscosity index exceeds 160, low temperature viscosity tends to be increased
to reduce the fuel efficiency at low oil temperatures. Moreover, startability tends
to be reduced.
[0042] The sulfur content of the lubricating base oil used in the present embodiment depends
on the sulfur content of the raw material. For example, in the case where a raw material
containing substantially no sulfur as a synthetic wax component obtained by the Fischer-Tropsch
reaction or the like is used, the lubricating base oil containing substantially no
sulfur can be obtained. In the case where a raw material containing sulfur such as
slack wax obtained in the refining process of the lubricating base oil and microcrystalline
wax obtained in the wax refining process thereof is used, the sulfur content of the
lubricating base oil to be obtained is usually 100 mass ppm or more. In the lubricating
base oil according to the present embodiment, from the viewpoint of further improvement
in heat and oxidation stability and a reduction in sulfur, it is preferable that the
sulfur content be 100 mass ppm or less, it is more preferable that the sulfur content
be 50 mass ppm or less, it is still more preferable that the sulfur content be 10
mass ppm or less, and it is particularly preferable that the sulfur content be 5 mass
ppm or less.
[0043] The nitrogen content of the lubricating base oil used in the present embodiment is
preferably 7 mass ppm or less, more preferably 5 mass ppm or less, and still more
preferably 3 mass ppm or less. If the nitrogen content exceeds 5 mass ppm, heat and
oxidation stability tends to be reduced. The nitrogen content in the present invention
means the nitrogen content measured according to JIS K 2609-1990.
[0044] It is preferable that %C
p of the lubricating base oil used in the present embodiment be 70 or more. %C
p is preferably 80 or more, more preferably 85 or more, still more preferably 87 or
more, and particularly preferably 90 or more. %C
p is preferably 99.9 or less, more preferably 98 or less, still more preferably 96
or less, and particularly preferably 94 or less. If %C
p of the lubricating base oil is less than the lower limit value, viscosity-temperature
properties, heat and oxidation stability, and friction properties tend to be reduced;
furthermore, if an additive is blended with the lubricating base oil, the effect of
the additive tends to be reduced. If %C
p of the lubricating base oil exceeds the upper limit value, the solubility of the
additive tends to be reduced.
[0045] It is preferable that %C
A of the lubricating base oil used in the present embodiment be 2 or less. %C
A is more preferably 1 or less, still more preferably 0.8 or less, and particularly
preferably 0.5 or less. If %C
A of the lubricating base oil exceeds the upper limit value, viscosity-temperature
properties, heat and oxidation stability, and fuel efficiency tend to be reduced.
[0046] It is preferable that %C
N of the lubricating base oil used in the present embodiment be 30 or less. %C
N is preferably 25 or less, more preferably 20 or less, still more preferably 15 or
less, and particularly preferably 10 or less. %C
N is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more,
and particularly preferably 6 or more. If %C
N of the lubricating base oil exceeds the upper limit value, viscosity-temperature
properties, heat and oxidation stability, and friction properties tend to be reduced.
If %C
N is less than the lower limit value, the solubility of the additive tends to be reduced.
[0047] %C
P, %C
N, and %C
A in the present invention mean the percentage of the number of paraffin carbon atoms
to the total number of carbon atoms, the percentage of the number of naphthene carbon
atoms to the total number of carbon atoms, and the percentage of the number of aromatic
carbon atoms to the total number of carbon atoms, respectively, which are determined
by the method (n-d-M ring analysis) according to ASTM D 3238-85. Namely, preferable
ranges of %C
P, %C
N, and %C
A above described are based on the values determined by the method above; for example,
even in a lubricating base oil containing no naphthene content, %C
N determined by the method may indicate a value more than 0.
[0048] The content of the saturates in the lubricating base oil used in the present embodiment
is preferably 90% by mass or more, preferably 95% by mass or more, more preferably
99% by mass or more based on the total amount of the lubricating base oil; the proportion
of the cyclic saturates in the saturates is preferably 40% by mass or less, preferably
35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or
less, and still more preferably 21% by mass or less. The proportion of the cyclic
saturates in the saturates is preferably 5% by mass or more, and more preferably 10%
by mass or more. If the content of the saturates and the proportion of the cyclic
saturates in the saturates each satisfy the conditions above, viscosity-temperature
properties and heat and oxidation stability can be improved; if an additive is blended
with the lubricating base oil, the function of the additive can be demonstrated at
a higher level while the additive is sufficiently stably dissolved in the lubricating
base oil. Furthermore, according to the present embodiment, the friction properties
of the lubricating base oil itself can be improved; as a result, an improvement in
a friction reducing effect and thus an improvement in energy saving properties can
be attained.
[0049] The saturates in the present invention are measured by the method described in ASTM
D 2007-93 above.
[0050] In the method for separating the saturates or in composition analysis of the cyclic
saturates, a noncyclic saturates, or the like, a similar method that can obtain similar
results can be used. Examples of the methods, besides the method above, can include
the method described in ASTM D 2425-93, the method described in ASTM D 2549-91, the
method by a high performance liquid chromatography (HPLC), or the modified methods
thereof.
[0051] The aromatic content of the lubricating base oil used in the present embodiment is
preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably
2% by mass or less, and particularly preferably 1% by mass or less based on the total
amount of the lubricating base oil, and is preferably 0.1% by mass or more, and more
preferably 0.2% by mass or more based on the total amount of the lubricating base
oil. If the content of the aromatics exceeds the upper limit value, viscosity-temperature
properties, heat and oxidation stability, friction properties, anti-volatilization,
and low temperature viscosity properties tend to be reduced; if an additive is blended
with the lubricating base oil, the effect of the additive tends to be reduced. The
lubricating base oil according to the present embodiment may be a lubricating base
oil containing no aromatics, but the content of the aromatics in the range of the
lower limit value or more can further enhance the solubility of the additive.
[0052] The aromatic content in the present invention means the value measured according
to ASTM D 2007-93. The aromatics usually include alkylbenzene and alkylnaphthalene;
anthracene, phenanthrene, and alkylated products thereof; compounds in which four
or more benzene rings are condensed; and aromatic compounds having a heteroatom such
as pyridines, quinolines, phenols, and naphthols.
[0053] A synthetic base oil may be used as the lubricating base oil according to the present
embodiment. Examples of the synthetic base oil having a kinematic viscosity at 100°C
of 1 to 10 mm
2/s include poly-α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof,
isoparaffin, alkylbenzene, alkylnaphthalene, diesters (such as ditridecyl glutarate,
di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-ethylhexylcebacate),
polyol esters (such as trimethylolpropane caprylate, trimethylolpropane pelargonate,
pentaerythritol 2-ethylhexanoate, and pentaerythritol pelargonate), polyoxyalkylene
glycol, dialkyldiphenyl ether, polyphenyl ether; among these, poly-α-olefins are preferable.
Examples of poly-α-olefins typically include oligomers or co-oligomers of α-olefins
having a carbon number of 2 to 32, preferably a carbon number of 6 to 16 (such as
1-octene oligomer, decene oligomer, and ethylene-propylene co-oligomer) and hydrides
thereof.
[0054] The method for producing poly-α-olefin is not particularly limited, and examples
thereof include a method for polymerizing α-olefin in the presence of a polymerization
catalyst containing a complex of aluminum trichloride or boron trifluoride, water,
an alcohol (such as ethanol, propanol, and butanol), and carboxylic acid or an ester
thereof, such as a Friedel-Crafts catalyst.
[0055] In the lubricating oil composition according to the present embodiment, the lubricating
base oil according to the present embodiment may be used alone, or the lubricating
base oil according to the present embodiment may be used in combination with one or
two or more of other base oils. In the case where the lubricating base oil according
to the present embodiment is used in combination with the other base oil(s), it is
preferable that the proportion of the lubricating base oil according to the present
embodiment in the mixed base oils be 30% by mass or more, it is more preferable that
the proportion of the lubricating base oil according to the present embodiment in
the mixed base oils be 50% by mass or more, and it is still more preferable that the
proportion of the lubricating base oil according to the present embodiment in the
mixed base oils be 70% by mass or more.
[0056] The other base oils used in combination with the lubricating base oil according to
the present embodiment is not particularly limited, and examples of a mineral oil-based
base oil include solvent refined mineral oils, hydrocracked mineral oils, hydrorefined
mineral oils, and solvent dewaxed base oils having a kinematic viscosity at 100°C
of 10 mm
2/s or more and 1000 mm
2/s or less.
[0057] Examples of the other synthetic base oils used in combination with the lubricating
base oil according to the present embodiment include the synthetic base oils described
above having a kinematic viscosity at 100°C of out of the range of 1 to 10 mm
2/s.
[0058] Moreover, the lubricating oil composition according to the present embodiment contains
a branched poly(meth)acrylate viscosity index improver (A) (hereinafter referred to
as "viscosity index improver according to the present embodiment" for convenience)
containing one or two or more structural units represented by the following formula
(1) in the proportion of 30 to 90 mol% and having a branching degree of 0.1 to 8.0.
Thereby, the fuel efficiency, the maintenance of fuel efficiency, and the durability
can be enhanced more significantly compared to the case where the present configuration
is not included. The compound has any form as long as the compound satisfies the condition
that the compound is a branched poly(meth)acrylate viscosity index improver containing
the structural unit represented by the following formula (1) in the proportion of
30 to 90 mol% and having the branching degree of 0.1 to 8.0. Specific examples of
the compound can include non-dispersive or dispersive poly(meth)acrylate viscosity
index improvers, (meth)acrylate-olefin copolymers, or a mixture thereof.

[wherein R
1 represents hydrogen or a methyl group, and R
2 represents a linear or branched hydrocarbon group having a carbon number of 6 or
less.]
[0059] R
2 in the structural unit represented by the formula (1), as described above, is a linear
or branched hydrocarbon group having a carbon number of 6 or less and may be one hydrocarbon
group or a mixture of two or more thereof; R
2 is preferably a linear or branched hydrocarbon having a carbon number of 4 or less,
still more preferably a linear or branched hydrocarbon having a carbon number of 3
or less, and more preferably a hydrocarbon group having a carbon number of 2 or less.
[0060] In the viscosity index improver according to the present embodiment, the proportion
of the (meth)acrylate structural unit represented by the formula (1) in a polymer
is 30 to 90 mol% as described above, preferably 85 mol% or less, more preferably 80
mol% or less, still more preferably 75 mol% or less, and particularly preferably 70
mol% or less. The proportion is preferably 30 mol% or more, more preferably 35 mol%
or more, and still more preferably 40 mol% or more. At a proportion more than 90 mol%,
the solubility in the base oil, the effect of improving viscosity temperature properties,
and low temperature viscosity properties may be inferior; at a proportion less than
30 mol%, the effect of improving viscosity temperature properties may be inferior.
[0061] It is preferable that the viscosity index improver according to the present embodiment
be the viscosity index improver (A) containing one or two or more structural units
represented by the following formula (2) in the proportion of 0.1 to 50 mol%.

[wherein R
3 represents hydrogen or a methyl group, and R
4 represents a linear or branched hydrocarbon group having a carbon number of 16 or
more.]
[0062] It is preferable that as described above, R
4 in the structural unit represented by the formula (2) be one linear or branched hydrocarbon
group having a carbon number of 16 or more or a mixture of two or more thereof, it
is more preferable that R
4 in the structural unit represented by the formula (2) be a linear or branched hydrocarbon
group having a carbon number of 17 or more, and it is still more preferable that R
4 in the structural unit represented by the formula (2) be a linear or branched hydrocarbon
group having a carbon number of 18 or more.
[0063] Further, in the viscosity index improver according to the present embodiment, the
proportion of the (meth)acrylate structural unit represented by the formula (2) in
the polymer is preferably 0.1 to 50 mol% as described above, more preferably 45 mol%
or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or
less, and most preferably 30 mol% or less. The proportion is more preferably 0.2 mol%
or more, more preferably 1 mol% or more, still more preferably 5 mol% or more, particularly
preferably 10 mol% or more, and most preferably 20 mol% or more. At a proportion more
than 50 mol%, the effect of improving viscosity temperature properties may be inferior;
at a proportion less than 0.1 mol%, the solubility in the base oil, low temperature
viscosity properties, and the effect of improving viscosity temperature properties
may be inferior.
[0064] Besides the (meth)acrylate structural unit represented by the formula (1) and the
formula (2) preferably used, the viscosity index improver according to the present
embodiment may be a copolymer having any (meth)acrylate structural unit. Such a copolymer
can be prepared by copolymerizing one or two or more of monomers represented by the
following formula (3) (hereinafter referred to as "Monomer (M-1)"), one or two or
more of monomers represented by the following formula (4) (hereinafter referred to
as "Monomer (M-2)", and a monomer other than Monomer (M-1) and Monomer (M-2):

[wherein R
1 represents a hydrogen atom or a methyl group, and R
2 represents a linear or branched hydrocarbon group having a carbon number of 6 or
less.]

[wherein R
3 represents a hydrogen atom or a methyl group, and R
4 represents a linear or branched hydrocarbon group having a carbon number of 16 or
more.]
[0065] Any monomer can be used in combination with Monomer (M-1) and Monomer (M-2), and
a monomer represented by the following formula (5) (hereinafter referred to as "Monomer
(M-3)") is suitable, for example. A copolymer of Monomer (M-1), Monomer (M-2), and
Monomer (M-3) is a non-dispersive poly(meth)acrylate viscosity index improver.

[wherein R
5 represents a hydrogen atom or a methyl group; and R
6 represents a linear or branched hydrocarbon group having a carbon number of 7 or
more and 15 or less.].
[0066] R
6 in the structural unit represented by the formula (5) is a linear or branched hydrocarbon
group having a carbon number of 7 or more and 15 or less, preferably a linear or branched
hydrocarbon having a carbon number of 10 or more, more preferably a linear or branched
hydrocarbon having a carbon number of 11 or more, and still more preferably a branched
hydrocarbon group having a carbon number of 12 or more.
[0067] In the viscosity index improver according to the present embodiment, the (meth)acrylate
structural unit represented by the formula (5) in the polymer may be one or two or
more mixtures, and it is preferable that the proportion be 60 mol% or less, the proportion
is more preferably 50 mol% or less, still more preferably 45 mol% or less, particularly
preferably 40 mol% or less, and most preferably 30 mol% or less. At a proportion more
than 60 mol%, the effect of improving viscosity temperature properties and low temperature
viscosity properties may be inferior; at a proportion less than 0.5 mol%, the effect
of improving viscosity temperature properties may be inferior.
[0068] It is suitable that the other monomers used in combination with Monomers (M-1) and
(M-2) be one or two or more selected from the monomer represented by the following
formula (6) (hereinafter referred to as "Monomer (M-4)") and the monomer represented
by the following formula (7) (hereinafter referred to as "Monomer (M-5)"). A copolymer
of Monomers (M-1) and (M-2) with Monomers (M-4) and/or (M-5) is the so-called dispersive
poly(meth)acrylate viscosity index improver. The dispersive poly(meth)acrylate viscosity
index improver may further contain Monomer (M-3) as the constitutional monomer.

[wherein R
5 represents a hydrogen atom or a methyl group, R
6 represents an alkylene group having a carbon number of 1 to 18, E
1 represents an amine residue or heterocycle residue having 1 to 2 nitrogen atoms and
0 to 2 oxygen atoms, and a represents 0 or 1.]
[0069] Examples of the alkylene group having a carbon number of 1 to 18 represented by R
6 specifically can include an ethylene group, a propylene group, a butylene group,
a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene
group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group,
a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene
group, and an octadecylene group (these alkylene groups may be linear or branched).
[0070] Examples of the group represented by E
1 specifically can include a dimethylamino group, a diethylamino group, a dipropylamino
group, a butylamino group, an anilino group, a toluidino group, a xylidino group,
an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group,
a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a
piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an
imidazolino group, and a pyrazino group.

[wherein R
7 represents a hydrogen atom or a hydrocarbon group, and E
2 represents a hydrocarbon group or an amine residue or heterocycle residue having
1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.]
[0071] Examples of the group represented by E
2 specifically can include a dimethylamino group, a diethylamino group, a dipropylamino
group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group,
an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group,
a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a
piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an
imidazolino group, and a pyrazino group.
[0072] Preferable examples of Monomers (M-4) and (M-5) specifically can include dimethylaminomethyl
methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl
methacrylate, 2-methyl-5-vinyl pyridine, morpholinomethyl methacrylate, morpholinoethyl
methacrylate, N-vinylpyrrolidone, and mixtures thereof.
[0073] The copolymerization molar ratio of a copolymer of Monomers (M-1) and (M-2) and Monomers
(M-3) to (M-5) is not particularly limited, and Monomers (M-1) and (M-2):Monomers
(M-2) to (M-4) = 20:80 to 90:10 or so is preferable, and the ratio is more preferably
30:70 to 80:20, and still more preferably 40:60 to 70:30.
[0074] The method for producing the viscosity index improver according to the present embodiment
is not particularly limited, and examples thereof include a method in which using
a control radical polymerization process, an alkyl methacrylate serving as an arm
portion (polymerization chain of alkyl methacrylate) is polymerized, and the polyalkyl
methacrylate is then reacted with a polyfunctional compound having two or more ethylenic
unsaturated double bonds.
[0075] The control radical polymerization process involves an atom transfer radical polymerization
(ATRP) process, a reversible addition-fragmentation chain transfer (RAFT) process,
or a nitroxide mediated polymerization process.
[0079] The synthesis can be performed as a batch operation, a semi-batch operation, a continuous
step, a feed step, or a bulk step. The synthesis can be performed in an emulsion,
a solution, or a suspension.
[0080] In the synthesis, by changing the amounts of an initiator and the polyfunctional
compound having two or more ethylenic unsaturated double bonds to be used, the average
molecular weight of the polymethacrylate or viscosity index improver to be obtained
can be adjusted.
[0081] The reaction rate to the viscosity index improver using the synthesized arm portion
is 70% or more, preferably 80% or more, and more preferably 85% or more based on the
amount of the polymer reacted to become the viscosity index improver. If the reaction
rate is low, the arm portion remains, and the molecular weight cannot be increased.
[0082] The PSSI (Permanent Shear Stability Index) of the viscosity index improver according
to the present embodiment in a diesel injector method is 5 or less, and preferably
3 or less. If the PSSI exceeds this range, shear stability is poor, and to keep the
kinematic viscosity and the HTHS viscosity after usage at a constant level or more,
the initial fuel efficiency may be reduced.
[0083] The "PSSI in the diesel injector method" here means the permanent shear stability
index of the polymer (Permanent Shear Stability Index) calculated based on the data
measured by ASTM D 6278-02 (Test Method for Shear Stability of Polymer Containing
Fluids Using a European Diesel Injector Apparatus) in accordance with ASTM D 6022-01
(Standard Practice for Calculation of Permanent Shear Stability Index).
[0084] It is preferable that the weight average molecular weight (M
W) of the viscosity index improver according to the present embodiment be 100,000 or
more, and the weight average molecular weight is more preferably 200,000 or more,
still more preferably 300,000 or more, and particularly preferably 400,000 or more.
It is preferable that the weight average molecular weight be 1,000,000 or less, and
the weight average molecular weight is more preferably 900,000 or less, still more
preferably 700,000 or less, and particularly preferably 600,000 or less. If the weight
average molecular weight is less than 100,000, the effect of improving a viscosity
index when the viscosity index improver is dissolved in the lubricating base oil is
small; not only fuel efficiency and low temperature viscosity properties are inferior
but also cost may increase. If the weight average molecular weight exceeds 1,000,000,
the effect of increasing viscosity is excessively increased; not only fuel efficiency
and low temperature viscosity properties are inferior, but also shear stability, the
solubility in the lubricating base oil, and storage stability are reduced.
[0085] The ratio of the weight average molecular weight to the PSSI in the diesel injector
method of the viscosity index improver according to the present embodiment (M
W/PSSI) is 2.0 × 10
4 or more, preferably 5.0 × 10
4 or more, and particularly preferably 8.0 × 10
4 or more. If M
W/PSSI is less than this range, fuel efficiency and low temperature startability, namely,
viscosity temperature properties and low temperature viscosity properties may be reduced.
[0086] It is preferable that the ratio (M
W/M
N) of the weight average molecular weight (M
W) to the number average molecular weight (M
N) of the viscosity index improver according to the present embodiment be 5.0 or less,
and the ratio is more preferably 4.0 or less, still more preferably 3.5 or less, particularly
preferably 3.0 or less, and most preferably 2.0 or less. It is preferable that M
W/M
N be 1.0 or more, and the ratio is more preferably 1.1 or more, and still more preferably
1.2 or more. If M
W/M
N is 4.0 or more or 1.0 or less, solubility and the effect of improving viscosity temperature
properties may be reduced so that sufficient storage stability and fuel efficiency
cannot be maintained.
[0087] The degree of branching of the viscosity index improver according to the present
embodiment is 0.1 to 8.0, more preferably 6.0 or less, more preferably 4.0 or less,
still more preferably 3.0 or less, particularly preferably 2.5 or less, and most preferably
2.0 or less. The degree of branching is preferably 0.2 or more, more preferably 0.5
or more, and still more preferably 1.0 or more. If the degree of branching exceeds
8.0, viscosity temperature properties and fuel efficiency may be reduced. If the degree
of branching is less than 0.1, viscosity temperature properties and fuel efficiency
are reduced and shear stability and durability may be reduced.
[0088] The "degree of branching" in the present invention means the ratio of the number
of carbon atoms derived from a monomer that forms the main chain which is the longest
atom chain in the molecule to the number of carbon atoms derived from a monomer that
forms an arm branched therefrom (the number of carbon atoms in arm portion/the number
of carbon atoms that form the main chain).
[0089] For example, for a star polymethacrylate, the number of carbon atoms derived from
a monomer that forms the main chain which is the longest atom chain in the molecule
designates the number of carbon atoms in the two longest arm portions, and the number
of carbon atoms derived from a monomer that forms an arm branched portion designates
the number of carbon atoms in the other arm portions. The degree of branching is a
value calculated based on the number of carbon atoms of the arm portion, and the number
of carbon atoms of the core portion is not included.
[0090] The following formula schematically shows an example of a star polymer. The star
polymer has 6 arm portions connected to the core portion, the number of carbon atoms
of the longest arm portion is A, and the number of carbon atoms of the second longest
arm portion is B. The degree of branching in this case is (C + D + E + F)/(A + B).

[0091] The content of the viscosity index improver according to the present embodiment is
preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, still more preferably
1 to 30% by mass, particularly preferably 5 to 20% by mass based on the total amount
of the composition. If the content of the viscosity index improver is less than 0.1%
by mass, the effect of improving the viscosity index and the effect of reducing the
viscosity of a product are reduced, and fuel efficiency may not be improved. At a
content more than 50% by mass, the cost of the product is significantly increased,
and the viscosity of the base oil needs to be reduced; for this reason, the lubrication
performance under severe lubrication conditions (high temperature high shear conditions)
may be reduced, causing deficits such as wear, seizure, and fatigue breaking.
[0092] Besides the viscosity index improver according to the present embodiment, the lubricating
oil composition according to the present embodiment may further contain a conventional
general non-dispersive or dispersive poly(meth)acrylate, a non-dispersive or dispersive
ethylene-α-olefin copolymer or a hydride thereof, a polyisobutylene or a hydride thereof,
a styrene-diene hydrogenation copolymer, a styrene-maleic anhydride ester copolymer,
polyalkylstyrene and the like.
[0093] The content of the viscosity index improver in the lubricating oil composition according
to the present embodiment is 0.1 to 50% by mass based on the total amount of the composition,
and the content is preferably 0.5 to 20% by mass, more preferably 1.0 to 15% by mass,
and still more preferably 1.5 to 12% by mass based on the total amount of the composition.
If the content is less than 0.1% by mass, low temperature properties may be insufficient;
if the content exceeds 50% by mass, the shear stability of the composition may be
reduced.
[0094] It is preferable that the lubricating oil composition according to the present embodiment
contain a friction modifier (B). Thereby, fuel efficiency performance can be increased
compared to the case where the present configuration is not included. Examples of
the friction modifier (B) include one or more friction modifiers selected from organic
molybdenum compounds and ash-free friction modifiers.
[0095] Examples of organic molybdenum compounds used in the present embodiment can include
organic molybdenum compounds containing sulfur such as molybdenum dithiophosphate,
molybdenum dithiocarbamate (MoDTC); complexes of molybdenum compounds (such as molybdenum
oxides such as molybdenum dioxide and molybdenum trioxide; molybdic acids such as
ortho-molybdic acid, para-molybdic acid, and (poly)molybdic acid sulfide; metal salts
thereof; molybdates such as ammonium salts thereof; molybdenum sulfides such as molybdenum
disulfide, molybdenum trisulfide, molybdenum pentasulfide, and molybdenum polysulfide;
molybdenum sulfide acid and metal salts or amine slats thereof; and molybdenum halides
such as molybdenum chloride) with sulfur-containing organic compounds (such as alkyl(thio)xanthate,
thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbylthiuram disulfide,
bis(di(thio)hydrocarbyldithiophosphonate) disulfide, organic (poly)sulfides, and sulfurized
esters), or other organic compounds; or complexes of sulfur-containing molybdenum
compounds such as molybdenum sulfide and molybdenum sulfide acid with alkenyl succinimides.
[0096] For the organic molybdenum compound, organic molybdenum compounds containing no sulfur
as a constitutional element can be used. Examples of the organic molybdenum compounds
containing no sulfur as a constitutional element specifically include molybdenum-amine
complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and
molybdenum salts of alcohols; among these, molybdenum-amine complexes, molybdenum
salts of organic acids, and molybdenum salts of alcohols are preferable.
[0097] In the lubricating oil composition according to the present embodiment, if the organic
molybdenum compound is used, its content is not particularly limited; the content
is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still
more preferably 0.01% by mass or more, and particularly preferably 0.03% by mass or
more, and preferably 0.2% by mass or less, more preferably 0.1% by mass or less, still
more preferably 0.08% by mass or less, and particularly preferably 0.06% by mass or
less based on the total amount of the lubricating oil composition in terms of the
molybdenum element. If the content is less than 0.001% by mass, the effect of reducing
friction by addition thereof tends to be insufficient, and the fuel efficiency and
heat and oxidation stability of the lubricating oil composition tend to be insufficient.
If the content exceeds 0.2% by mass, the effect corresponding to the content is not
obtained, and the storage stability of the lubricating oil composition tends to be
reduced.
[0098] As the ash-free friction modifier, any compound usually used as a friction modifier
for a lubricating oil can be used, and examples thereof include compounds having a
carbon number of 6 to 50 and containing one or two or more hetero elements selected
from an oxygen atom, a nitrogen atom, and a sulfur atom in the molecule. More specifically,
examples thereof include ash-free friction modifiers such as amine compounds, fatty
acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic ethers,
urea compounds, and hydrazide compounds having at least one alkyl group or alkenyl
group having a carbon number of 6 to 30, particularly linear alkyl group having a
carbon number of 6 to 30, a linear alkenyl group, a branched alkyl group, and a branched
alkenyl group in the molecule.
[0099] The content of the ash-free friction modifier in the lubricating oil composition
according to the present embodiment is preferably 0.01% by mass or more, more preferably
0.1% by mass or more, and still more preferably 0.3% by mass or more, and preferably
3% by mass or less, more preferably 2% by mass or less, and still more preferably
1% by mass or less based on the total amount of the lubricating oil composition. If
the content of the ash-free friction modifier is less than 0.01% by mass, the effect
of reducing friction by addition thereof tends to be insufficient; at a content more
than 3% by mass, the effect such as anti-wear additives is readily inhibited, or the
solubility of the additive tends to be reduced.
[0100] In the present embodiment, it is preferable that the friction modifier (B) be an
organic molybdenum friction modifier, it is more preferable that the friction modifier
(B) be an organic molybdenum compound containing sulfur, and it is still more preferable
that the friction modifier (B) be molybdenum dithiocarbamate.
[0101] To further improve the performance, any additives usually used in the lubricating
oil can be contained in the lubricating oil composition according to the present embodiment
according to the purpose. Examples of such additives can include additives such as
metallic detergents, ash-free dispersants, anti-wear agents (or extreme-pressure agents),
antioxidants, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators,
and antifoaming agents.
[0102] If these additives are contained in the lubricating oil composition according to
the present embodiment, it is preferable that the content of each additive be 0.01
to 10% by mass based on the total amount of the lubricating oil composition.
[0103] It is preferable that the kinematic viscosity at 100°C of the lubricating oil composition
according to the present embodiment be 4 to 12 mm
2/s, and kinematic viscosity is preferably 9.0 mm
2/s or less, more preferably 8.0 mm
2/s or less, still more preferably 7.0 mm
2/s or less, and particularly preferably 6.8 mm
2/s or less. The kinematic viscosity at 100°C of the lubricating oil composition according
to the present embodiment is preferably 4.5 mm
2/s or more, more preferably 5.0 mm
2/s or more, still more preferably 5.5 mm
2/s or more, and particularly preferably 6.0 mm
2/s or more. The kinematic viscosity at 100°C here designates a kinematic viscosity
at 100°C specified in ASTM D-445. If the kinematic viscosity at 100°C is less than
4 mm
2/s, insufficient lubrication may be caused; at a kinematic viscosity more than 12
mm
2/s, necessary low temperature viscosity and sufficient fuel efficiency performance
may not be obtainable.
[0104] It is preferable that the kinematic viscosity at 40°C of the lubricating oil composition
according to the present embodiment be 4 to 50 mm
2/s, and the kinematic viscosity is preferably 40 mm
2/s or less, more preferably 35 mm
2/s or less, particularly preferably 30 mm
2/s or less, and most preferably 28 mm
2/s or less. The kinematic viscosity at 40°C of the lubricating oil composition according
to the present embodiment is preferably 15 mm
2/s or more, more preferably 18 mm
2/s or more, still more preferably 20 mm
2/s or more, particularly preferably 22 mm
2/s or more, and most preferably 25 mm
2/s or more. The kinematic viscosity at 40°C here designates a kinematic viscosity
at 40°C specified in ASTM D-445. If the kinematic viscosity at 40°C is less than 4
mm
2/s, insufficient lubrication may be caused; at a kinematic viscosity more than 50
mm
2/s, necessary low temperature viscosity and sufficient fuel efficiency performance
may not be obtainable.
[0105] It is preferable that the viscosity index of the lubricating oil composition according
to the present embodiment be in the range of 140 to 400, and the viscosity index is
preferably 180 or more, more preferably 190 or more, still more preferably 200 or
more, particularly preferably 210 or more, and most preferably 215 or more. If the
viscosity index of the lubricating oil composition according to the present embodiment
is less than 140, it may be difficult to improve fuel efficiency while maintaining
the HTHS viscosity at 150°C, and to reduce the low temperature viscosity at -35°C.
If the viscosity index of the lubricating oil composition according to the present
embodiment is 400 or more, evaporation properties may be reduced, and deficits due
to insufficient solubility of the additive and matching properties with a seal material
may be caused.
[0106] It is preferable that the HTHS viscosity at 100°C of the lubricating oil composition
according to the present embodiment be 5.5 mPa·s or less, and the HTHS viscosity is
more preferably 5.0 mPa·s or less, still more preferably 4.7 mPa·s or less, particularly
preferably 4.5 mPa·s or less, and most preferably 4.4 mPa·s or less. The HTHS viscosity
is preferably 3.0 mPa·s or more, still more preferably 3.5 mPa·s or more, particularly
preferably 4.0 mPa·s or more, and most preferably 4.1 mPa·s or more. The HTHS viscosity
at 100°C in the present embodiment designates a high temperature high shear viscosity
at 100°C specified in ASTM D4683. If the HTHS viscosity at 100°C is less than 3.0
mPa·s, insufficient lubrication may be caused; at an HTHS viscosity more than 5.5
mPa·s, necessary low temperature viscosity and sufficient fuel efficiency performance
may not be obtainable.
[0107] It is preferable that the HTHS viscosity at 150°C of the lubricating oil composition
according to the present embodiment be less than 4.0 mPa·s, and the HTHS viscosity
is more preferably 2.7 mPa·s or less, still more preferably 2.5 mPa·s or less, and
particularly preferably 2.4 mPa·s or less. The HTHS viscosity is preferably 2.0 mPa·s
or more, more preferably 2.1 mPa·s or more, still more preferably 2.2 mPa·s or more,
and particularly preferably 2.3 mPa·s or more. The HTHS viscosity at 150°C here designates
a high temperature high shear viscosity at 150°C specified in ASTM D4683. If the HTHS
viscosity at 150°C is less than 2.0 mPa·s, insufficient lubrication may be caused;
at an HTHS viscosity more than 4.0 mPa·s, sufficient fuel efficiency performance may
not be obtainable.
[0108] It is preferable that the ratio of the HTHS viscosity at 150°C to HTHS viscosity
at 100°C of the lubricating oil composition according to the present embodiment (HTHS
viscosity at 150°C/HTHS viscosity at 100°C) be 0.50 or more, and the ratio is more
preferably 0.52 or more, still more preferably 0.53, and particularly preferably 0.54
or more. If the ratio is less than 0.50, necessary low temperature viscosity and sufficient
fuel efficiency performance may not be obtainable.
[0109] The lubricating oil composition according to the present embodiment can sufficiently
reduce the kinematic viscosity at 40°C, kinematic viscosity at 100°C and HTHS viscosity
at 100°C in an engine oil having a HTHS viscosity at 150°C of less than 2.6 mPa·s,
can sufficiently suppress an increase in the coefficient of friction in the boundary
lubrication region, and has high fuel efficiency. The lubricating oil composition
according to the present embodiment having such high properties can be suitably used
as energy saving engine oils such as energy saving gasoline engine oils and energy
saving diesel engine oils.
Examples
[0110] Hereinafter, the present invention will be more specifically described based on Examples
and Comparative Example, but the present invention will not be limited to Examples
below.
(Synthesis Example 1: synthesis of Non-dispersive PMA viscosity index improver A-1)
<Synthesis of arm molecule>
[0111] To a 300 ml 5-necked separable flask having an anchor metallic stirring blade (with
a vacuum seal), a Dimroth condenser, a 3-necked cock for introducing nitrogen, and
a sample introduction port mounted thereon, 25.2 parts by mass of methyl methacrylate,
36.5 parts by mass of methacrylate in which R
4 in the formula (3) was an alkyl group having a carbon number of 18, and 120 parts
by mass of a hydrocarbon solvent (SAE10) as a solvent were placed, and a uniform solution
was prepared under stirring. The solution was cooled to 0°C with an ice bath, and
vacuum degassing/nitrogen purging of the reaction system was performed 5 times using
a diaphragm pump. Under a nitrogen stream, 0.27 parts by mass of azobisisobutyronitrile
(AIBN) as a radical initiator, 0.013 parts by mass of 1,4-cyclohexadiene, and 0.11
parts by mass of iodine were charged from the sample introduction port; then, polymerization
was performed under a nitrogen atmosphere at a solution temperature of 80°C for 12
hours to prepare an arm molecule solution.
[0112] As a result of GPC analysis (standard substance: polystyrene), the weight average
molecular weight of the obtained arm molecule was 87400, the number average molecular
weight (Mn) was 62000, and the degree of dispersion (Mw/Mn) was 1.41.
<Synthesis of star polymer>
[0113] To the arm solution, 0.07 parts by mass of azobisisobutyronitrile (AIBN) and 2.14
parts by mass of ethylene glycol dimethacrylate were added, and polymerization was
performed under a nitrogen atmosphere at a solution temperature of 80°C for 12 hours
to prepare a solution of a target star polymer (hereinafter referred to as "Non-dispersive
PMA viscosity index improver A-1").
[0114] As a result of GPC analysis (standard substance: polystyrene), the weight average
molecular weight (Mw) of the obtained Non-dispersive PMA viscosity index improver
A-1 was 570000, the number average molecular weight (Mn) was 470000, the degree of
dispersion (Mw/Mn) was 1.23, PSSI was 3.8, and Mw/PSSI was 1.5 × 10
5. The arm conversion rate of the Non-dispersive PMA viscosity index improver A-1 was
64% by mass, the average number of arms was 8, and the degree of branching was 3.0.
[0115] Here, the arm conversion rate and the average number of arms are values calculated
based on the following expressions, respectively.

[0116] The weight average molecular weight and the number average molecular weight are the
weight average molecular weight and the number average molecular weight in terms of
polystyrene measured by using an HLC-8220 GPC apparatus made by Tosoh Corporation
having 3 TSKgel Super MultiPore HZ-M columns made by Tosoh Corporation (4.6 mm ID
× 15 cm) in series and tetrahydrofuran as a solvent at a temperature of 40°C, a flow
rate of 0.35 mL/min, a sample concentration of 1% by mass, an amount of sample injection
of 5 µL with a detector deference refractive index meter (RI).
(Synthesis Example 2: synthesis of Non-dispersive PMA viscosity index improver A-2)
[0117] A star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver
A-2") was synthesized in the same manner as in Synthesis Example 1 except that instead
of the arm molecule solution in Synthesis Example 1, an arm molecule solution containing
an arm molecule including 70 mol% methyl methacrylate and 30 mol% methacrylate in
which R4 in the formula (4) was an alkyl group having a carbon number of 18 (weight
average molecular weight: 54000, number average molecular weight (Mn): 42000, degree
of dispersion (Mw/Mn): 1.29) was used.
[0118] The Mw of Non-dispersive PMA viscosity index improver A-2 obtained was 490000, Mn
was 410000, Mw/Mn was 1.19, PSSI was 2.2, Mw/PSSI was 2.2 × 10
5, and the degree of branching was 3.9.
(Synthesis Example 3: synthesis of Non-dispersive PMA viscosity index improver A-3)
[0119] A star polymer (hereinafter referred to as "Non-dispersive PMA viscosity index improver
A-3") was synthesized in the same manner as in Synthesis Example 1 except that instead
of the arm molecule solution in Synthesis Example 1, an arm molecule solution containing
an arm molecule including 70 mol% methyl methacrylate and 30 mol% methacrylate in
which R4 in the formula (4) was an alkyl group having a carbon number of 18 (weight
average molecular weight: 85000, number average molecular weight (Mn): 60000, degree
of dispersion (Mw/Mn): 1.42) was used.
[0120] The Mw of Non-dispersive PMA viscosity index improver A-3 obtained was 450000, Mn
was 380000, Mw/Mn was 1.19, PSSI was 3.0, Mw/PSSI was 1.5 × 10
5, and the degree of branching was 2.0.
(Examples 1 to 5, Comparative Examples 1 to 4)
[0121] In Examples 1 to 5 and Comparative Examples 1 to 4, base oils and additives shown
below were used to prepare lubricating oil compositions having compositions shown
in Table 2. The properties of Base oils O-1, O-2, and O-3 are shown in Table 1.
(Base oils)
[0122]
O-1 (Base oil 1): mineral oil prepared by hydrocracking /hydrogenation isomerization
of a n-paraffin containing oil
O-2 (Base oil 2): hydrocracked mineral oil
O-3 (Base oil 3): hydrocracked mineral oil
(Additives)
[0123]
A-1: non-dispersive PMA viscosity index improver (copolymer prepared by reacting 70
mol% methyl methacrylate, 30 mol% methacrylate in which R2 in the formula (3) was an alkyl group having a carbon number of 18, a small amount
of a polymerization initiator, and glycol dimethacrylate. Mw = 570000, Mn = 470000,
Mw/Mn = 1.23, PSSI = 3.8, Mw/PSSI = 1.5 × 105, degree of branching = 3.0)
A-2: non-dispersive PMA viscosity index improver (copolymer prepared by reacting 70
mol% methyl methacrylate, 30 mol% methacrylate in which R2 in the formula (3) was an alkyl group having a carbon number of 18, a small amount
of a polymerization initiator, and glycol dimethacrylate. Mw = 490000, Mn = 410000,
Mw/Mn = 1.19, PSSI = 2.2, Mw/PSSI = 2.2 × 105, degree of branching = 3.9)
A-3: non-dispersive PMA viscosity index improver (copolymer prepared by reacting 70
mol% methyl methacrylate, 30 mol% methacrylate in which R2 in the formula (3) was an alkyl group having a carbon number of 18, a small amount
of a polymerization initiator, and glycol dimethacrylate. Mw = 450000, Mn = 380000,
Mw/Mn = 1.19, PSSI = 3.0, Mw/PSSI = 1.5 × 105, degree of branching = 2.0)
a-1: non-dispersive PMA viscosity index improver (copolymer prepared by reacting 70
mol% methyl methacrylate, 30 mol% methacrylate in which R2 in the formula (3) was an alkyl group having a carbon number of 18, a small amount
of a polymerization initiator, and glycol dimethacrylate. Mw = 620000, Mn = 440000,
Mw/Mn = 1.41, PSSI = 5.7, Mw/PSSI = 1.1 × 105, degree of branching = 9.0)
a-2: dispersive PMA viscosity index improver (copolymer prepared by reacting 20 mol%
methyl methacrylate, 80 mol% methacrylate in which R2 in the formula (3) was an alkyl
group having a carbon number of 12 to 15, and small amounts of a dispersive group
and a polymerization initiator. Mw = 300000, Mn = 70000, Mw/Mn = 4.0, PSSI = 40, Mw/PSSI
= 7.5 × 103, degree of branching = 0)
a-3: dispersive PMA viscosity index improver (copolymer prepared by reacting 20 mol%
methyl methacrylate, 80 mol% methacrylate in which R2 in the formula (3) was an alkyl group having a carbon number of 12 to 15, and small
amounts of a dispersive group and a polymerization initiator. Mw = 80000, Mn = 30000,
Mw/Mn = 2.7, PSSI = 10, Mw/PSSI = 8.0 × 103, degree of branching = 0)
B-1: MoDTC (alkyl group chain length: C8/C13, Mo content: 10 mass%, sulfur content:
11 mass%)
B-2: glycerol monooleate C-1: other additives (such as a succinimide dispersant, ZnDTP,
an antioxidant, an anti-wear agent, a pour-point depressant, and an antifoaming agent).
[Table 1]
| |
|
O-1 |
O-2 |
O-3 |
| |
|
Base oil 1 |
Base oil 2 |
Base oil 3 |
| Density (15°C) |
g/cm3 |
0.820 |
0.835 |
0.8320 |
| Kinematic viscosity (40°C) |
mm2/s |
15.8 |
20.0 |
13.5 |
| (100°C) |
mm2/s |
3.85 |
4.29 |
3.27 |
| Viscosity index |
|
141 |
123 |
112 |
| Pour point |
°C |
-22.5 |
-17.5 |
-22.5 |
| Aniline point |
°C |
119 |
116 |
109 |
| Iodine number |
|
0.06 |
0.05 |
5.38 |
| Sulfur content |
mass ppm |
<1 |
<1 |
<1 |
| Nitrogen content |
mass ppm |
<3 |
<3 |
<3 |
| n-d-M analysis |
%CP |
93.3 |
80.7 |
72.6 |
| |
%CN |
6.7 |
19.3 |
23.4 |
| |
%CA |
0 |
0 |
0 |
| Separation by chromatography mass% |
Saturate content |
99.6 |
99.7 |
99.6 |
| |
Aromatic content |
0.2 |
0.2 |
0.3 |
| |
Resin content |
0.1 |
0.1 |
0.1 |
| |
Recover rate |
99.9 |
100 |
100 |
| Paraffin content based on saturate content |
mass% |
87.1 |
53.8 |
50.7 |
| Naphthene content based on saturate content |
mass% |
12.9 |
46.2 |
49.3 |
[Evaluation of lubricating oil composition]
[0124] In the lubricating oil compositions in Examples 1 to 4 and Comparative Examples 1
to 3, the kinematic viscosity at 40°C or 100°C, the viscosity index, the HTHS viscosity
at 100°C or 150°C, and the viscosity reduction rate after the ultrasonic shear test
were measured.
- (1) Kinematic viscosity: ASTM D-445
- (2) Viscosity index: JIS K 2283-1993
- (3) HTHS viscosity: ASTM D-4683
- (4) Ultrasonic shear test: according to JASO M347-95, an output was adjusted with
Standard oil A specified in the ASTM test method, and a shear test was performed at
an amplitude of 28 µm, the vibration number of 10 KHz, an irradiation time of 10 minutes,
and a sample volume of 60 mL to measure the kinematic viscosity at 100°C and calculate
the viscosity reduction rate.
[Table 2]
| Base oil |
Based on total amount of base oil |
|
|
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
| O-1 |
Base oil 1 |
|
% by mass |
50 |
|
|
|
|
|
|
| O-2 |
Base oil 2 |
|
% by mass |
|
50 |
50 |
50 |
50 |
50 |
50 |
| O-3 |
Base oil 3 |
|
% by mass |
50 |
50 |
50 |
50 |
50 |
50 |
50 |
| |
Viscosity of base oil (40°C) |
mm2/s |
14.7 |
16.2 |
16.2 |
16.2 |
16.2 |
16.2 |
16.2 |
| |
Viscosity of base oil (100°C) |
|
3.6 |
3.7 |
3.7 |
3.7 |
3.7 |
3.7 |
3.7 |
| |
Viscosity index of base oil |
|
124 |
117 |
117 |
117 |
117 |
117 |
117 |
| Additives |
Based on total amount of composition |
|
|
|
|
|
|
|
|
| A-1 |
Viscosity index improver 1 (degree of branching 3.0) |
% by mass |
9.9 |
9.0 |
|
|
|
|
|
| A-2 |
Viscosity index improver 2 (degree of branching 3.9) |
% by mass |
|
|
10.3 |
|
|
|
|
| A-3 |
Viscosity index improver 3 (degree of branching 2.0) |
% by mass |
|
|
|
9.1 |
|
|
|
| a-1 |
Viscosity index improver 4 (degree of branching 9.0) |
% by mass |
|
|
|
|
9.9 |
|
|
| a-2 |
Viscosity index improver 6 (degree of branching 0) |
% by mass |
|
|
|
|
|
5.1 |
|
| a-3 |
Viscosity index improver 7 (degree of branching 0) |
% by mass |
|
|
|
|
|
|
5.9 |
| B-1 |
MoDTC |
|
% by mass |
0.7 |
0.7 |
0.7 |
0.7 |
0.7 |
0.7 |
0.7 |
| C-1 |
Other additives |
|
% by mass |
10 |
10 |
10 |
10 |
10 |
10 |
10 |
| Results of evaluation |
|
|
|
|
|
|
|
|
|
|
| Kinematic viscosity |
|
40°C |
mm2/s |
25.8 |
27.4 |
28.2 |
26.8 |
30.4 |
34.6 |
33.1 |
| |
|
100°C |
mm2/s |
6.45 |
6.52 |
6.58 |
6.37 |
7.22 |
8.1 |
7.1 |
| Viscosity index |
|
|
|
220 |
206 |
201 |
203 |
215 |
222 |
186 |
| HTHS viscosity |
|
100°C |
mPa·s |
4.32 |
4.43 |
4.68 |
4.37 |
5.01 |
4.86 |
5.03 |
| HTHS viscosity |
|
150°C |
mPa·s |
2.40 |
2.40 |
2.40 |
2.40 |
2.40 |
2.40 |
2.41 |
| HTHS viscosity (150°C)/HTHS viscosity (100°C) |
|
0.56 |
0.54 |
0.51 |
0.55 |
0.48 |
0.49 |
0.48 |
| Viscosity reduction rate after ultrasonic shear |
|
% |
3.6 |
3.5 |
2.0 |
2.6 |
5.3 |
20.6 |
7.0 |
[0125] As shown in Table 2, the lubricating oil compositions in Examples 1 to 4 containing
the component (A) show that the kinematic viscosity and the HTHS viscosity at 100°C
are low, a viscosity reduction rate after the ultrasonic shear test is small, the
fuel efficiency and the durability after usage are higher than those in the lubricating
oil composition in Comparative Example 1 in which the viscosity index improver having
a branching degree of more than 8.0 is blended, and the lubricating oil compositions
in Comparative Examples 2 and 3 in which the C6 or less methacrylate containing ratio
is low and the degree of branching is 0.