FIELD
[0001] The present invention relates to a lubricant composition. More specifically, the
present invention relates to a lubricant composition for an internal combustion engine,
particularly a lubricant composition for a gasoline engine.
BACKGROUND
[0002] Lubricant compositions are widely used in the automotive field for internal combustion
engines, automatic transmissions, gear oils and the like. In recent years, such lubricant
compositions are demanded to have a reduced viscosity for improving the fuel efficiency;
however, since a reduction in viscosity leads to a reduced oil film thickness, friction
cannot be sufficiently reduced. Accordingly, molybdenum dithiocarbamate (MoDTC) capable
of reducing friction by yielding molybdenum disulfide under boundary lubrication conditions
has been conventionally used. In such cases, MoDTC is usually used in combination
with a calcium-based detergent (e.g., Japanese Unexamined Patent Publication (Kokai)
No.
2013-199594 (PTL 1)). However, this combination has a limitation in reducing friction and thus
cannot sufficiently improve the fuel efficiency.
[0003] It is also known to use a magnesium-based detergent as a detergent (e.g., Japanese
Unexamined Patent Publication (Kokai) No.
2011-184566 (PTL 2) and Japanese Unexamined Patent Publication (Kokai) No.
2006-328265 (PTL 3)). The use of a magnesium-based detergent can reduce friction more than the
use of a calcium-based detergent; however, it has a problem of being likely to cause
wear.
[CITATION LIST]
[PATENT LITERATURE]
[0004]
[PTL 1] Japanese Unexamined Patent Publication (Kokai) No. 2013-199594
[PTL 2] Japanese Unexamined Patent Publication (Kokai) No. 2011-184566
[PTL 3] Japanese Unexamined Patent Publication (Kokai) No. 2006-328265
SUMMARY
[TECHNICAL PROBLEM]
[0005] An object of the present invention is to provide a lubricant composition capable
of reducing friction while ensuring anti-wear properties even at a reduced viscosity,
preferably a lubricant composition used in an internal combustion engine, more preferably
a lubricant composition used in a supercharged gasoline engine.
[SOLUTION TO PROBLEM]
[0006] The present inventors intensively studied to discover that the above-described object
can be achieved by adding a specific amount of at least one metal salicylate selected
from calcium salicylate and magnesium salicylate and a specific amount of a molybdenum-based
friction modifier to a lubricant base oil.
[0007] In other words, the present invention is a lubricant composition containing: a lubricant
base oil; (A1) a metal salicylate; and (B) a molybdenum-based friction modifier,
wherein
the amount of component (B) is in a range of 500 to 1,500 ppm by weight in terms of
a concentration [B] in ppm by weight of molybdenum in the lubricant composition,
component (A1) is any one of calcium salicylate, magnesium salicylate, and a combination
thereof,
the amount of calcium salicylate is 0 to 1,800 ppm by weight in terms of a concentration
[Ca] in ppm by weight of calcium derived from calcium salicylate in the lubricant
composition,
the amount of magnesium salicylate is 0 to 1,800 ppm by weight in terms of a concentration
[Mg] in ppm by weight of magnesium derived from magnesium salicylate in the lubricant
composition, and
a total of [Ca] and [Mg] is in a range of 200 to 3,000 ppm by weight.
[0008] In a preferable embodiment of the present invention, the lubricant composition further
includes at least one of following characteristic features (1) to (10):
- (1) the lubricant composition comprising (A) a metallic detergent, wherein the lubricant
composition comprises the metal salicylate (A1) in an amount of 5 to 100% by weight
based on the total weight of component (A) in terms of a ratio of [Ca] and [Mg] based
on a total concentration [A] in ppm by weight of metals derived from the metallic
detergent in the lubricant composition;
- (2) the lubricant composition optionally further comprises a metallic detergent other
than component (A1) as the metallic detergent (A), wherein the weight of component
(A1) based on the total weight of the metallic detergent (A) is in a range of 5 to
100% by weight;
- (3) the metal salicylate (A1) is magnesium salicylate and calcium salicylate;
- (4) the metal salicylate (A1) is at least one kind of magnesium salicylate;
- (5) the lubricant composition further comprises (A2) a metallic detergent other than
component (A1) as the metallic detergent (A), component (A2) comprises at least one
selected from magnesium, calcium and sodium, and the total content of the metallic
detergent (A) satisfies following equation (1):

wherein [A] represents a total concentration in ppm by weight of magnesium, calcium
and sodium in the lubricant composition;
- (6) the content of the metal salicylate (A1) satisfies following equation (2):

wherein [A1] represents a total concentration ([Ca] + [Mg]) in ppm by weight of magnesium
and calcium that are derived from component (A1) in the lubricant composition;
- (7) the CCS viscosity at -35°C is 6.2 Pa·s or less;
- (8) the high-temperature high-shear viscosity (HTHS viscosity) at 150°C is 1.7 to
2.9 mPa·s;
- (9) the kinematic viscosity at 100°C is less than 9.3 mm2/s; and
- (10) the lubricant composition is for an internal combustion engine.
[0009] The present invention also relates to a method of reducing friction while maintaining
low-wear properties by using the above-described lubricant composition or the lubricant
composition according to any one of embodiments (1) to (10).
[ADVANTAGEOUS EFFECTS OF INVENTION]
[0010] The lubricant composition of the present invention is capable of reducing friction
while ensuring anti-wear properties even at a reduced viscosity, and can thus be suitably
used as a lubricant composition for internal combustion engines, particularly as a
lubricant composition for supercharged gasoline engines.
DESCRIPTION OF EMBODIMENTS
Lubricant Base Oil
[0011] In the present invention, the lubricant base oil is not particularly restricted.
The lubricant base oil may be any one of mineral oils and synthetic oils, and these
oils can be used singly or as a mixture.
[0012] Examples of mineral oils include oils obtained by distilling an atmospheric residue,
which is generated by atmospheric distillation of crude oil, under reduced pressure
and refining the resulting lubricant fraction by one or more treatments, such as solvent
deasphalting, solvent extraction, hydrocracking, solvent dewaxing, and hydrorefining;
wax-isomerized mineral oils; GTL (Gas-to-Liquid) base oils; ATL (Asphalt-to-Liquid)
base oils; vegetable oil-derived base oils; and mixed base oils thereof.
[0013] Examples of the synthetic oils include polybutenes and hydrogenated products thereof;
poly-
α-olefins, such as 1-octene oligomer and 1-decene oligomer, and hydrogenated products
thereof; monoesters, such as 2-ethylhexyl laurate, 2-ethylhexyl palmitate, and 2-ethylhexyl
stearate; diesters, such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl
adipate, ditridecyl adipate, and di-2-ethylhexyl sebacate; polyol esters, such as
neopentyl glycol di-2-ethylhexanoate, neopentyl glycol di-
n-octanoate, neopentyl glycol di-
n-decanoate, trimethylolpropane tri-
n-octanoate, trimethylolpropane tri-
n-decanoate, pentaerythritol tetra-
n-pentanoate, pentaerythritol tetra-
n-hexanoate, and pentaerythritol tetra-2-ethylhexanoate; aromatic synthetic oils, such
as alkylnaphthalenes, alkylbenzenes, and aromatic esters; and mixtures thereof.
[0014] The kinematic viscosity (mm
2/s) at 100°C of the lubricant base oil is not particularly restricted; however, it
is preferably 2 to 15 mm
2/s, more preferably 3 to 10 mm
2/s, still more preferably 3 to 8 mm
2/s, most preferably 3 to 6 mm
2/s. By this, a lubricant composition which not only sufficiently forms an oil film
and provides excellent lubricity but also has less evaporation loss can be obtained.
[0015] The viscosity index (VI) of the lubricant base oil is not particularly restricted;
however, it is preferably 100 or higher, more preferably 120 or higher, most preferably
130 or higher. By this, the viscosity at low temperatures can be reduced while securing
an oil film at high temperatures.
(A) Metallic Detergent
(A1) Metal Salicylate
[0016] The lubricant composition of the present invention is characterized by comprising,
as a metallic detergent (A), a metal salicylate (A1) which is calcium salicylate,
magnesium salicylate or a combination thereof in the below-described specific range
of amount. The lubricant composition of the present invention may further comprise
other metallic detergent than calcium salicylate and magnesium salicylate as the metallic
detergent (A), and it is appropriate that the weight ratio of component (A1) based
on the total weight of the metallic detergent (A) be in a range of 5 to 100% by weight,
preferably 10 to 100% by weight, more preferably 15 to 100% by weight, particularly
preferably 20 to 100% by weight, most preferably 50 to 100% by weight, in terms of
a ratio of [Ca] and [Mg] based on a total concentration [A] in ppm by weight of metals
derived from the metallic detergent in the lubricant composition, wherein [Ca] is
a concentration in ppm by weight of calcium derived from calcium salicylate in the
lubricant composition, and [Mg] is a concentration in ppm by weight of magnesium derived
from magnesium salicylate in the lubricant composition. By containing at least one
selected from calcium salicylate and magnesium salicylate in a specific amount as
the metallic detergent, the lubricant composition can ensure high-temperature detergency
and rust inhibition that are required as a lubricant. In addition, the lubricant composition
can reduce friction and, therefore, can reduce torque. This is advantageous particularly
from the standpoint of fuel efficiency characteristics.
[0017] As for the amount of component (A1) in the lubricant composition of the present invention,
the amount of calcium salicylate is 0 to 1,800 ppm by weight, preferably 0 to 1,600
ppm by weight, in terms of the concentration [Ca] in ppm by weight of calcium in the
lubricant composition; the amount of magnesium salicylate is 0 to 1,800 ppm by weight,
preferably 0 to 1,600 ppm by weight, in terms of the concentration [Mg] in ppm by
weight of magnesium in the lubricant composition; and the value of [Ca] + [Mg] is
in a range of 200 to 3,000 ppm by weight, preferably 300 to 2,500 ppm by weight, more
preferably 400 to 2,000 ppm by weight. When the amount of component (A1) is greater
than the above-described upper limit, excessive wear may occur and a sludge may be
generated, whereas when the amount of component (A1) is smaller than the above-described
lower limit, the friction-reducing effect is low.
[0018] In the present invention, as described above, at least one selected from magnesium
salicylate and calcium salicylate is indispensable as the metal salicylate. Only a
single kind of these metal salicylates may be used, or two or more kinds thereof may
be used in combination. A combination of magnesium salicylate and calcium salicylate,
or magnesium salicylate alone is preferable, and magnesium salicylate is more preferable.
[0019] When component (A1) is magnesium salicylate alone, it is appropriate that the content
thereof in terms of the concentration [Mg] in ppm by weight of magnesium derived from
magnesium salicylate in the lubricant composition be in a range of 200 to 1,800 ppm
by weight, preferably 250 to 1,500 ppm by weight, more preferably 300 to 1,200 ppm
by weight, most preferably 400 to 1,000 ppm. When component (A1) is calcium salicylate
alone, it is appropriate that the content thereof in terms of the concentration [Ca]
in ppm by weight of calcium derived from calcium salicylate in the lubricant composition
be in a range of 200 to 1,800 ppm by weight, preferably 300 to 1,600 ppm by weight,
more preferably 500 to 1,400 ppm by weight. When component (A1) is a combination of
magnesium salicylate and calcium salicylate, it is appropriate that a total of [Ca]
and [Mg] satisfy a range of 200 to 3,000 ppm by weight, preferably 300 to 2,500 ppm
by weight, more preferably 400 to 2,000 ppm by weight. Particularly, it is appropriate
that [Mg] be in a range of 100 to 1,600 ppm by weight, preferably 150 to 1,400 ppm
by weight, more preferably 200 to 1,200 ppm by weight, most preferably 300 to 1,000
ppm, and that [Ca] be in a range of 100 to 1,600 ppm by weight, preferably 300 to
1,500 ppm by weight, more preferably 500 to 1,400 ppm by weight.
[0020] The magnesium content in magnesium salicylate and the calcium content in calcium
salicylate are each preferably 0.5 to 20% by weight, more preferably 1 to 16% by weight,
most preferably 2 to 14% by weight. The amount of component (A1) to be added is adjusted
such that magnesium and calcium are incorporated into the lubricant composition in
the above-described respective ranges of amount.
[0021] In particular, the metal salicylate (A1) is preferably an overbased metal salicylate,
more preferably a combination of magnesium salicylate and calcium salicylate, especially
preferably overbased magnesium salicylate. By this, acid neutralization performance
required for a lubricant can be ensured. When overbased magnesium salicylate is used,
a neutral magnesium- or calcium-based detergent may be mixed therewith. When overbased
calcium salicylate is used, a neutral calcium-based detergent may be used in combination.
[0022] The total base number of the metal salicylate (A1) is not restricted; however, it
is preferably 20 to 600 mg KOH/g, more preferably 50 to 500 mg KOH/g, most preferably
100 to 450 mg KOH/g. By this, acid neutralization performance, high-temperature detergency
and rust inhibition that are required for a lubricant can be ensured. When two or
more metal salicylates are used as a mixture, the base number of the mixture is preferably
in the above-described range.
[0023] It is preferable that the amount of component (A1) in the lubricant composition satisfies
following equation (2):

[0024] In equation (2), [A1] represents a total concentration (i.e. [Ca] + [Mg]) in ppm
by weight of magnesium and calcium that are derived from the magnesium salicylate
and calcium salicylate (A1) in the lubricant composition, and [B] is as described
above.
[0025] The value of [A1]/[B] is preferably less than 3.0, more preferably less than 2, still
more preferably less than 1.8, particularly preferably less than 1.5. When the value
of [A1]/[B] is greater than the above-described upper limit, the torque-reducing effect
may be low. The lower limit value of [A1]/[B] is preferably 0.1, more preferably 0.2,
still more preferably 0.3.
[0026] In a preferable embodiment, as described above, the lubricant composition of the
present invention comprises only magnesium salicylate as the metal salicylate (A1),
or a combination of magnesium salicylate and calcium salicylate as component (A1).
The lubricant composition of the present invention may further contain (A2) a metallic
detergent other than the calcium salicylate and magnesium salicylate (A1) as the metallic
detergent (A). In this case, as described above, it is appropriate that the weight
ratio of component (A1) based on the total weight of the metallic detergent (A) be
5 to 100% by weight, preferably 10 to 100% by weight, more preferably 15 to 100% by
weight, particularly preferably 20 to 100% by weight, most preferably 50 to 100% by
weight, in terms the ratio of [Ca] and [Mg] based on the total concentration [A] in
ppm by weight of metals derived from the metallic detergent in the lubricant composition.
It is particularly appropriate that the percentage (% by weight) of magnesium salicylate
based on the total weight of the metallic detergent (A) be 5 to 100% by weight, preferably
10 to 80% by weight, more preferably 10 to 60% by weight, particularly preferably
10 to 40% by weight, in terms the percentage of [Mg] based on the total concentration
[A] in ppm by weight of metals derived from the metallic detergent in the lubricant
composition. In a more preferable embodiment, the lubricant composition of the present
invention comprises only magnesium salicylate, or only a combination of magnesium
salicylate and calcium salicylate, as the metallic detergent (A).
(A2) Metallic Detergent Other Than Metal Salicylate
[0027] In the lubricant composition of the present invention, as component (A2) which is
a metallic detergent other than the metal salicylate (A1), a conventionally known
metallic detergent containing at least one selected from magnesium, calcium and sodium
can be used in combination. Examples of component (A2) include metal sulfonates. A
metal sulfonate may be used singly, or two or more thereof may be used in combination.
By incorporating a metal sulfonate, high-temperature detergency and rust inhibition
that are required for a lubricant can be better ensured. The amount of component (A2)
varies depending on the amount of component (Al); however, it is preferably 0 to 5,000
ppm by weight, more preferably 0 to 2,000 ppm by weight, most preferably 0 to 1,000
ppm by weight, in terms of a concentration [A2] in ppm by weight of metals derived
from component (A2) in the lubricant composition.
[0028] Examples of the metal sulfonate include magnesium sulfonate, calcium sulfonate, and
sodium sulfonate.
[0029] Further, a commonly-used metallic detergent other than the above-described ones can
also be used within a range that does not adversely affect the effects of the present
invention. For example, magnesium phenate, calcium phenate, and/or a sodium-based
detergent may be incorporated. Sodium sulfonate, sodium phenate, and sodium salicylate
are preferable as the sodium-based detergent. These sodium-based detergent may be
used singly, or in combination of two or more thereof. By incorporating a sodium-based
detergent(s), high-temperature detergency and rust inhibition that are required for
a lubricant can be ensured. The sodium-based detergent(s) can be used in combination
with the above-described magnesium-based detergent and optional calcium-based detergent.
[0030] It is preferable that the total amount of the metallic detergent (A) in the lubricant
composition satisfy following equation (1):

[0031] In equation (1), [A] represents a total concentration in ppm by weight of magnesium,
calcium and sodium in the lubricant composition, and [B] represents a concentration
in ppm by weight of molybdenum in the lubricant composition.
[0032] The value of [A]/[B] is preferably 3.0 or less, more preferably 2.8 or less, still
more preferably 2.6 or less, yet still more preferably 2.5 or less. When the value
of [A]/[B] is greater than the above-described upper limit value, excessive wear may
occur. The lower limit value of [A]/[B] is preferably 0.2, more preferably 0.5, still
more preferably 1.
(B) Molybdenum-based Friction Modifier
[0033] The molybdenum-based friction modifier is not particularly restricted, and any conventionally
known molybdenum-based friction modifier can be used. Examples thereof include sulfur-containing
organic molybdenum compounds, such as molybdenum dithiophosphate (MoDTP) and molybdenum
dithiocarbamate (MoDTC); complexes of a molybdenum compound and a sulfur-containing
organic compound or other organic compound; and complexes of an alkenylsuccinimide
and a sulfur-containing molybdenum compound, such as molybdenum sulfide or sulfurized
molybdic acid. Examples of the molybdenum compound include molybdenum oxides, such
as molybdenum dioxide and molybdenum trioxide; molybdic acids, such as ortho-molybdic
acid, para-molybdic acid, and sulfurized (poly)molybdic acid; molybdates, such as
metal salts and ammonium salts of these molybdic acids; molybdenum sulfides, such
as molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, and molybdenum
polysulfide; sulfurized molybdic acid, and metal salts and amine salts thereof; and
molybdenum halides, such as molybdenum chloride. Examples of the sulfur-containing
organic compound include alkyl(thio)xanthate, thiaziazole, mercaptothiadiazole, thiocarbonate,
tetrahydrocarbyl thiuram disulfide, bis(di(thio)hydrocarbyldithiophosphonate)disulfide,
organic (poly)sulfides, and sulfurized esters. Particularly, organic molybdenum compounds,
such as molybdenum dithiophosphate (MoDTP) and molybdenum dithiocarbamate (MoDTC),
are preferable.
[0034] Molybdenum dithiocarbamate (MoDTC) is a compound represented by following formula
[I], and molybdenum dithiophosphate (MoDTP) is a compound represented by following
formula [II].

[0035] In above-described formulae [I] and [II], R
1 to R
8 may be the same or different from each other and each represent a monovalent hydrocarbon
group having 1 to 30 carbon atoms. The hydrocarbon group may be linear or branched.
Examples of the monovalent hydrocarbon group include linear or branched alkyl groups
having 1 to 30 carbon atoms; alkenyl groups having 2 to 30 carbon atoms; cycloalkyl
groups having 4 to 30 carbon atoms; and aryl groups, alkylaryl groups and arylalkyl
groups, which have 6 to 30 carbon atoms. In the arylalkyl groups, an alkyl group may
be bound at any position. More specifically, examples of the alkyl group include a
methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group,
a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl
group, a heptadecyl group, and an octadecyl group, as well as branched alkyl groups
thereof, among which alkyl groups having 3 to 8 carbon atoms are particularly preferable.
Further, X
1 and X
2 each represent an oxygen atom or a sulfur atom, and Y
1 and Y
2 each represent an oxygen atom or a sulfur atom.
[0036] As component (B), a sulfur-free organic molybdenum compound can also be used. Examples
thereof include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum
salts of organic acids, and molybdenum salts of alcohols.
[0037] Moreover, as the friction modifier (B) in the present invention, the trinuclear molybdenum
compounds described in
U.S. Patent No. 5,906,968 can be used as well.
[0038] Component (B) is added in such an amount that allows the concentration [B] in ppm
by weight of molybdenum in the lubricant composition to be in a range of 500 to 1,500
ppm by weight, preferably 600 to 1,200 ppm by weight. When the amount of component
(B) is greater than the above-described upper limit, the detergency may be deteriorated,
whereas when the amount of component (B) is less than the above-described lower limit,
there are cases where friction cannot be sufficiently reduced or the detergency is
deteriorated.
[0039] As described above for component (A), the amount of component (B) preferably satisfies
following equation (1):

[0040] In equation (1), [A] represents a total concentration in ppm by weight of magnesium,
calcium and sodium in the lubricant composition, and [B] represents a concentration
in ppm by weight of molybdenum in the lubricant composition.
[0041] The value of [A]/[B] is preferably 3.0 or less, more preferably 2.8 or less, still
more preferably 2.6 or less, yet still more preferably 2.5 or less. The lower limit
value of [A]/[B] is preferably 0.2, more preferably 0.5, still more preferably 1.0.
[0042] As described above for component (A1), the amount of component (B) preferably satisfies
following equation (2):

[0043] In equation (2), [A1] represents a concentration in ppm by weight of metal(s) derived
from component (A1) in the lubricant composition. The value of [A1]/[B] is preferably
less than 3.0, more preferably less than 2.0, still more preferably less than 1.8,
particularly preferably less than 1.5. When the value of [A1]/[B] is greater than
the above-described upper limit, the torque-reducing effect may be low. The lower
limit value of [A1]/[B] is preferably 0.1, more preferably 0.2, still more preferably
0.3.
[0044] In the lubricant composition of the present invention, the above-described lubricant
base oil and components (A1) and (B) are indispensable, and the lubricant composition
may also comprise conventionally known anti-wear agent, ashless dispersant and viscosity
index improver as optional components.
[0045] As the anti-wear agent, conventionally known anti-wear agents can be used. Thereamong,
a phosphorus-containing anti-wear agent is preferable, and a zinc dithiophosphate
(ZnDTP (also referred to as "ZDDP")) represented by the following formula is particularly
preferable.

[0046] In this formula, R
1 and R
2 may be the same or different from each other and each represent a hydrogen atom or
a monovalent hydrocarbon group having 1 to 26 carbon atoms. The monovalent hydrocarbon
group is a primary or secondary alkyl group having 1 to 26 carbon atoms; an alkenyl
group having 2 to 26 carbon atoms; a cycloalkyl group having 6 to 26 carbon atoms;
an aryl, alkylaryl or arylalkyl group having 6 to 26 carbon atoms; or a hydrocarbon
group containing an ester bond, ether bond, alcohol group or carboxyl group. R
1 and R
2 are each preferably a primary or secondary alkyl group having 2 to 12 carbon atoms,
a cycloalkyl group having 8 to 18 carbon atoms or an alkylaryl group having 8 to 18
carbon atoms, and R
1 and R
2 may be the same or different from each other. Particularly, R
1 and R
2 are each preferably a zinc dialkyldithiophosphate, and the primary alkyl group has
preferably 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. The secondary
alkyl group has preferably 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms.
The above-described zinc dithiophosphate may be used singly, or two or more thereof
may be used as a mixture. In addition, zinc dithiocarbamate (ZnDTC) may be used in
combination.
[0047] Further, at least one compound selected from phosphate-based and phosphite-based
phosphorus compounds represented by following formulae (3) and (4) as well as metal
salts and amine salts thereof can also be used.

[0048] In above-described formula (3), R
3 represents a monovalent hydrocarbon group having 1 to 30 carbon atoms; R
4 and R
5 each independently represent a hydrogen atom or a monovalent hydrocarbon group having
1 to 30 carbon atoms; and m represents 0 or 1.

[0049] In above-described formula (4), R
6 represents a monovalent hydrocarbon group having 1 to 30 carbon atoms; R
7 and R
8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having
1 to 30 carbon atoms; and n represents 0 or 1.
[0050] In formulae (3) and (4), examples of the monovalent hydrocarbon groups having 1 to
30 carbon atoms that are represented by R
3 to R
8 include alkyl groups, cycloalkyl groups, alkenyl groups, alkyl-substituted cycloalkyl
groups, aryl groups, alkyl-substituted aryl groups, and arylalkyl groups. Particularly,
R
3 to R
8 are each preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having
6 to 24 carbon atoms, more preferably an alkyl group having 3 to 18 carbon atoms,
most preferably an alkyl group having 4 to 15 carbon atoms.
[0051] Examples of the phosphorus compounds represented by formula (3) include phosphorous
acid monoesters and hydrocarbyl phosphonites, which have one of the above-described
hydrocarbon groups having 1 to 30 carbon atoms; phosphorous acid diesters, monothiophosphorous
acid diesters and (hydrocarbyl)phosphonous acid monoesters, which have two of the
above-described hydrocarbon groups having 1 to 30 carbon atoms; phosphorous acid triesters
and (hydrocarbyl)phosphonous acid diesters, which have three of the above-described
hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof.
[0052] Metal salts or amine salts of the phosphorus compounds represented by formula (3)
or (4) can be obtained by allowing, for example, a metal base (e.g., a metal oxide,
a metal hydroxide, a metal carbonate, or a metal chloride) or a nitrogen compound
(e.g., ammonia, or an amine compound having only a hydrocarbon group or hydroxyl group-containing
hydrocarbon group having 1 to 30 carbon atoms in the molecule), to act on a phosphorus
compound represented by formula (3) or (4) and subsequently neutralizing some or all
of residual acidic hydrogens. Examples of a metal in the above-described metal base
include alkali metals, such as lithium, sodium, potassium, and cesium; alkaline earth
metals, such as calcium, magnesium, and barium; and heavy metals (excluding molybdenum),
such as zinc, copper, iron, lead, nickel, silver, and manganese. Thereamong, alkaline
earth metals, such as calcium and magnesium, and zinc are preferable, and zinc is
particularly preferable.
[0053] In the lubricant composition, the anti-wear agent is incorporated in an amount of
usually 0.1 to 5.0% by weight, preferably 0.2 to 3.0% by weight.
[0054] Examples of the ashless dispersant include nitrogen-containing compounds having at
least one linear or branched alkyl or alkenyl group having 40 to 500 carbon atoms,
preferably 60 to 350 carbon atoms, in the molecule, and derivatives thereof; Mannich
dispersants; mono- or bis-succinimides (e.g., alkenylsuccinimides); benzylamines having
at least one alkyl or alkenyl group having 40 to 500 carbon atoms in the molecule;
polyamines having at least one alkyl or alkenyl group having 40 to 400 carbon atoms
in the molecule; and modified products thereof obtained by modification with a boron
compound, carboxylic acid, phosphoric acid or the like. Any one or more of these ashless
dispersants can be arbitrarily selected and incorporated. It is particularly preferable
that the lubricant composition comprise an alkenylsuccinimide.
[0055] A method of producing the above-described succinimides is not particularly restricted
and, for example, and the succinimides can be obtained by allowing a compound having
an alkyl or alkenyl group having 40 to 500 carbon atoms to react with maleic anhydride
at 100 to 200°C and subsequently allowing the resulting alkyl succinate or alkenyl
succinate to react with a polyamine. Examples of the polyamine include diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Examples
of the derivatives of nitrogen-containing compounds exemplified above as the ashless
dispersant include compounds modified with a so-called "oxygen-containing organic
compound", which are obtained by allowing a monocarboxylic acid having 1 to 30 carbon
atoms (e.g., a fatty acid), a polycarboxylic acid having 2 to 30 carbon atoms (e.g.,
oxalic acid, phthalic acid, trimellitic acid, or pyromellitic acid) or an anhydride
thereof, an ester compound thereof, an alkylene oxide having 2 to 6 carbon atoms,
or a hydroxy(poly)oxyalkylene carbonate to act on the above-described nitrogen-containing
compounds and subsequently neutralizing or amidating some or all of residual amino
groups and/or imino groups; so-called "boron-modified compounds", which are obtained
by allowing boric acid to act on the above-described nitrogen-containing compounds
and subsequently neutralizing or amidating some or all of residual amino groups and/or
imino groups; so-called "phosphate-modified compounds", which are obtained by allowing
phosphoric acid to act on the above-described nitrogen-containing compounds and subsequently
neutralizing or amidating some or all of residual amino groups and/or imino groups;
sulfur-modified compounds obtained by allowing a sulfur compound to act on the above-described
nitrogen-containing compounds; and modified compounds obtained by performing a combination
of two or more types of modifications selected from modification with an oxygen-containing
organic compound, boron modification, phosphate modification and sulfur modification
on the above-described nitrogen-containing compounds. Among these derivatives, boric
acid-modified compounds of alkenylsuccinimides, particularly boric acid-modified compounds
of bis-type alkenylsuccinimides, can further improve the heat resistance when used
in combination with the above-described base oil.
[0056] The amount of the ashless dispersant is 20% by weight or less, preferably 15% by
weight or less, still more preferably 5% by weight or less, based on the total amount
of the composition. As the ashless dispersant, a boron-containing ashless dispersant
can also be used as a mixture with a boron-free ashless dispersant. When a boron-containing
ashless dispersant is used, the content ratio thereof is not particularly restricted;
however, it is appropriate that the amount of boron contained in the composition be
preferably 0.001 to 0.2% by weight, more preferably 0.003 to 0.1% by weight, most
preferably 0.005 to 0.05% by weight, based on the total amount of the composition.
[0057] The number-average molecular weight (Mn) of the ashless dispersant is preferably
not less than 2,000, more preferably not less than 2,500, still more preferably not
less than 3,000, most preferably not less than 5,000, but preferably not higher than
15,000. When the number-average molecular weight of the ashless dispersant is less
than the above-described lower limit value, sufficient dispersibility is not attained
in some cases. Meanwhile, when the number-average molecular weight of the ashless
dispersant is higher than the above-described upper limit value, an excessively high
viscosity makes the fluidity insufficient, causing an increase in deposits.
[0058] Examples of the above-described viscosity index improver include those containing
a polymethacrylate, a dispersion-type polymethacrylate, an olefin copolymer (e.g.,
a polyisobutylene or an ethylene-propylene copolymer), a dispersion-type olefin copolymer,
a polyalkylstyrene, a hydrogenated styrene-butadiene copolymer, a styrene-maleic anhydride
ester copolymer, a star isoprene or the like. Further, a comb-shaped polymer which
contains, in its main chain, at least a repeating unit based on a polyolefin macromer
and a repeating unit based on an alkyl (meth)acrylate containing an alkyl group having
1 to 30 carbon atoms, can also be used.
[0059] The viscosity index improver is usually composed of the above-described polymer and
a diluent oil. The content of the viscosity index improver is preferably 0.01 to 20%
by weight, more preferably 0.02 to 10% by weight, most preferably 0.05 to 5% by weight,
in terms of the polymer amount based on the total amount of the composition. When
the content of the viscosity index improver is less than the above-described lower
limit value, the viscosity-temperature characteristics and the low-temperature viscosity
characteristics may be deteriorated. Meanwhile, when the content of the viscosity
index improver is higher than the above-described upper limit value, not only the
viscosity-temperature characteristics and the low-temperature viscosity characteristics
may be deteriorated, but also the production cost is largely increased.
[0060] In the lubricant composition of the present invention, in order to improve the performance
thereof, other additive(s) may further be incorporated in accordance with the intended
purpose. As other additives, additives that are commonly used in lubricant compositions
can be used, and examples thereof include an antioxidant, a friction modifier other
than above-described component (B), a corrosion inhibitor, a rust inhibitor, a pour-point
depressant, a demulsifier, a metal deactivator, and an anti-foaming agent.
[0061] Examples of the antioxidant include phenolic and amine-based ashless antioxidants,
and metal-based antioxidants, such as copper-based and molybdenum-based antioxidants.
Examples of the phenolic ashless antioxidants include 4,4'-methylene-bis(2,6-di-
tert-butylphenol), 4,4'-bis(2,6-di-
tert-butylphenol) and isooctyl-3-(3,5-di-
t-butyl-4-hydroxyphenyl)propionate, and examples of the amine-based ashless antioxidants
include phenyl-
α-naphthylamine, alkylphenyl-
α-naphthylamine, and dialkyldiphenylamine. The antioxidant is incorporated into the
lubricant composition usually in an amount of 0.1 to 5% by weight.
[0062] Examples of the friction modifier other than above-described component (B) include
esters, amines, amides, and sulfurized esters. The friction modifier is incorporated
into the lubricant composition usually in an amount of 0.01 to 3% by weight.
[0063] Examples of the corrosion inhibitor include benzotriazole-based, tolyltriazole-based,
thiadiazole-based, and imidazole-based compounds. Examples of the rust inhibitor include
petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenylsuccinic
acid esters, and polyhydric alcohol esters. The rust inhibitor and the corrosion inhibitor
are each incorporated into the lubricant composition usually in an amount of 0.01
to 5% by weight.
[0064] As the pour-point depressant, for example, a polymethacrylate-based polymer that
is compatible with the lubricant base oil to be used can be selected. The pour-point
depressant is incorporated into the lubricant composition usually in an amount of
0.01 to 3% by weight.
[0065] Examples of the demulsifier include polyalkylene glycol-based nonionic surfactants,
such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene
alkylnaphthyl ethers. The demulsifier is incorporated into the lubricant composition
usually in an amount of 0.01 to 5% by weight.
[0066] Examples of the metal deactivator include imidazolines, pyrimidine derivatives, alkylthiadiazoles,
mercaptobenzothiazoles, benzotriazoles and derivatives thereof, 1,3,4-thiadiazole
polysulfides, 1,3,4-thiadiazolyl-2,5-bisdialkyl dithiocarbamates, 2-(alkyldithio)benzimidazoles,
and
β-(o-carboxybenzylthio)propionitrile. The metal deactivator is incorporated into the
lubricant composition usually in an amount of 0.01 to 3% by weight.
[0067] Examples of the anti-foaming agent include silicone oils having a kinematic viscosity
at 25°C of 1,000 to 100,000 mm
2/s, alkenylsuccinic acid derivatives, esters of a polyhydroxy aliphatic alcohol and
a long-chain fatty acid, methyl salicylate, and
o-hydroxybenzyl alcohols. The anti-foaming agent is incorporated into the lubricant
composition usually in an amount of 0.001 to 1% by weight.
[0068] As other additive, an alkali borate-based additive can be added. The alkali borate-based
additive contains an alkali metal borate hydrate and can be represented by the following
formula:
M
2O·xB
2O
3·yH
2O
[0069] In this formula, M represents an alkali metal; x represents 2.5 to 4.5; and y represents
1.0 to 4.8.
[0070] Specific examples of the alkali borate-based additive include lithium borate hydrate,
sodium borate hydrate, potassium borate hydrate, rubidium borate hydrate and cesium
borate hydrate, among which potassium borate hydrate and sodium borate hydrate are
preferable, and potassium borate hydrate is particularly preferable. The average particle
size of these alkali metal borate hydrate particles is generally 1 micron (µ) or smaller.
In the alkali metal borate hydrate used in the present invention, the ratio of boron
to alkali metal is preferably in a range of about 2.5:1 to 4.5:1. The amount of the
alkali borate-based additive to be added is 0.002 to 0.05% by weight in terms of boron
amount based on the total amount of the lubricant composition.
[0071] The CCS viscosity at -35°C of the lubricant composition of the present invention
is not restricted; however, it is preferably 6.2 Pa·s or less, more preferably 5.0
Pa·s or less, still more preferably 4.0 Pa·s or less, most preferably 3.5 Pa·s or
less.
[0072] In the lubricant composition of the present invention, it is preferable that the
amount of molybdenum contained therein and the CCS viscosity at -35°C satisfy following
equation (5):

wherein [CCS viscosity] represents a value (Pa·s) of the CCS viscosity at -35°C of
the lubricant composition, and [B] represents the concentration in ppm by weight of
molybdenum in the lubricant composition.
[0073] The value of [CCS viscosity]/[B] is more preferably 0.008 or less, still more preferably
0.005 or less. When this value is larger than 0.01, the torque reduction ratio may
be reduced and the detergency may be deteriorated. The lower limit value of [CCS viscosity]/[B]
is not restricted; however, it is preferably 0.002, more preferably 0.003.
[0074] The high-temperature high-shear viscosity (HTHS viscosity) at 150°C of the lubricant
composition of the present invention is not restricted; however, it is preferably
1.7 to 2.9 mPa·s, more preferably 2.0 to 2.6 mPa·s.
[0075] The kinematic viscosity at 100°C of the lubricant composition of the present invention
is not restricted; however, it is preferably less than 9.3 mm
2/s, more preferably less than 8.2 mm
2/s.
[0076] The lubricant composition of the present invention has sufficient friction characteristics
and wear characteristics and exerts an effect of attaining a high torque reduction
ratio even at a low viscosity; therefore, the lubricant composition of the present
invention can be suitably used for internal combustion engines as well as supercharged
gasoline engines.
EXAMPLES
[0077] The present invention will now be described in more detail by way of Examples and
Comparative Examples thereof; however, the present invention is not restricted to
the below-described Examples.
[0078] Materials used in Examples and Comparative Examples are as follows.
Lubricant Base Oil
[0079] Lubricant base oil: Fischer-Tropsch-derived base oil, kinematic viscosity at 100°C
= 4.1 mm
2/s, VI = 127
(A) Metallic Detergents
(A1) Metal Salicylates
[0080]
(A1-1) magnesium salicylate (total base number: 340 mg KOH/g, magnesium content: 7.5%
by weight)
(A1-2) calcium salicylate 1 (total base number: 350 mg KOH/g, calcium content: 12.0%
by weight)
(A1-3) calcium salicylate 2 (total base number: 220 mg KOH/g, calcium content: 8.0%
by weight)
(A2) Metal Sulfonates
[0081]
(A2-1) magnesium sulfonate (total base number: 400 mg KOH/g, magnesium content: 9.0%
by weight)
(A2-2) calcium sulfonate (total base number: 300 mg KOH/g, calcium content: 11.6%
by weight)
(B) Molybdenum-based Friction Modifier
[0082] Molybdenum-based friction modifier: MoDTC (a compound represented by above-described
formula [1], wherein X
1 and X
2 are both O, and Y
1 and Y
2 are both S; molybdenum content: 10% by weight)
Anti-wear Agents
[0083]
Anti-wear agent 1: pri-ZnDTP (primary alkyl group)
Anti-wear agent 2: sec-ZnDTP (secondary alkyl group)
Other Additives
[0084]
Antioxidant: phenolic antioxidant
Ashless dispersant: succinimide
Viscosity index improver: polymethacrylate
Anti-foaming agent: dimethyl silicone
Examples 1 to 12 and Comparative Examples 1 to 8
[0085] Lubricant compositions were each prepared by mixing the respective components in
the amounts indicated in Tables 1 and 3. The amounts of the magnesium-based detergent,
calcium-based detergent and molybdenum-based friction modifier indicated in Tables
1 and 3 are concentrations in terms of the contents (ppm by weight) of magnesium,
calcium and molybdenum based on the total amount of each lubricant composition ([Mg],
[Ca] and [B] in the order mentioned), respectively. The amounts of the anti-wear agent
and other additives are in parts by weight based on the total amount (100 parts by
weight) of each lubricant composition. It is noted here that the amount of the magnesium-based
detergent and that of the calcium-based detergent were controlled such that the total
molar amount of magnesium and calcium contained in these detergents was as constant
as possible in all of Examples and Comparative Examples. For the thus obtained compositions,
the below-described tests were conducted. The results thereof are presented in Tables
2 and 4.
[0086] In Tables 1 and 3 below, [A] represents a total concentration in ppm by weight of
all magnesium and calcium contained in each lubricant composition (i.e. including
Mg and Ca derived from magnesium sulfonate and calcium sulfonate, respectively), and
[A1] represents a total concentration in ppm by weight of magnesium and calcium derived
from the metal salicylate(s) (A1) contained in each lubricant composition (i.e. [Ca]
+ [Mg]). Further, [A1]/[A] represents a ratio (% by weight) of [A1], which is the
total concentration in ppm by weight of magnesium and calcium derived from the metal
salicylate(s), based on [A], which is the total concentration in ppm by weight of
all magnesium and calcium contained in each lubricant composition.
(1) High-Temperature High-Shear Viscosity at 150°C (HTHS150)
[0087] The high-temperature high-shear viscosity at 150°C was measured in accordance with
ASTM D4683.
(2) CCS Viscosity at -35°C (CCS Viscosity)
[0088] The CCS viscosity at -35°C was measured in accordance with ASTM D5293.
(3) Kinematic Viscosity at 100°C (KV100)
[0089] The kinematic viscosity at 100°C was measured in accordance with ASTM D445.
(4) Torque Reduction Ratio
[0090] Using the lubricant compositions obtained in Examples and Comparative Examples as
test compositions, the torque was measured in a motoring test with a gasoline engine.
A TOYOTA 2ZR-FE 1.8L in-line 4-cylinder engine was used as the engine, and a torque
meter was arranged between a motor and the engine to measure the torque at an oil
temperature of 80°C and an engine speed of 700 rpm. The torque was also measured in
the same manner using a commercially available GF-5 0W-20 oil as a standard oil. The
torque (T) of each test composition was compared with the torque (T
0) of the standard oil, and the reduction ratio from the torque of the standard oil,
({(T
0 - T)/T
0} × 100) (%), was calculated. A higher reduction ratio indicates superior fuel efficiency.
A reduction ratio of 5.5% or higher was regarded as satisfactory.
(5) Diameter of Shell Wear Scar
[0091] The diameter of shell wear scar was measured in accordance with the shell four-ball
test (ASTM D4172), except that the rotation speed, the load, the testing temperature
and the testing time were set at 1,800 rpm, 40 kgf, 90°C and 30 minutes, respectively.
A wear scar diameter of 0.7 mm or smaller was regarded as satisfactory.
(6) Hot Tube Test (Evaluation of High-Temperature Detergency)
[0092] Each lubricant composition and air were allowed to continuously flow in a glass tube
of 2 mm in inner diameter for 16 hours at rates of 0.3 mL/hr and 10 mL/sec, respectively,
while maintaining the temperature of the glass tube at 270°C. A lacquer adhered to
the glass tube was compared with a color chart and evaluated with a score of 10 when
the lacquer was transparent or a score of 0 when the lacquer was black. A higher score
indicates superior high-temperature detergency. A score of 5.0 or higher was regarded
as satisfactory.
[Table 1]
|
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Example 10 |
Example 11 |
Example 12 |
Lubricant base oil |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
(A1-1) magnesium salicylate ([Mg], ppm by weight) |
300 |
600 |
300 |
0 |
300 |
1,100 |
300 |
0 |
900 |
600 |
600 |
1,500 |
(A2-1) magnesium sulfonate ([Mg], ppm by weight) |
0 |
0 |
0 |
300 |
0 |
0 |
0 |
300 |
0 |
0 |
0 |
0 |
(A1-2) calcium salicylate 1 ([Ca], ppm by weight) |
1,400 |
900 |
1,400 |
1,400 |
0 |
0 |
1,400 |
1,400 |
500 |
0 |
1,400 |
1,300 |
(A1-3) calcium salicylate 2 ([Ca], ppm by weight) |
0 |
0 |
0 |
0 |
1,400 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
(A2-2) calcium sulfonate ([Ca], ppm by weight) |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
900 |
0 |
0 |
[A1] total ([Ca] + [Mg]) |
1,700 |
1,500 |
1,700 |
1,400 |
1,700 |
1,100 |
1,700 |
1,400 |
1,400 |
600 |
2,000 |
2,800 |
[A1]/[A] (% by weight) |
100 |
100 |
100 |
82 |
100 |
100 |
100 |
82 |
100 |
40 |
100 |
100 |
(B) molybdenum-based friction modifier |
700 |
700 |
700 |
700 |
700 |
1,000 |
1,000 |
1,000 |
700 |
700 |
700 |
700 |
Anti-wear agent 1 |
1 |
1 |
- |
- |
- |
1 |
- |
- |
1 |
1 |
1 |
1 |
Anti-wear agent 2 |
- |
- |
1 |
1 |
1 |
- |
1 |
1 |
- |
- |
- |
- |
Antioxidant |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
Ash-free dispersant |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
Viscosity index improver |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
Anti-foaming agent |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
[A]/[B] |
2.4 |
2.1 |
2.4 |
2.4 |
2.4 |
1.1 |
1.7 |
1.7 |
2.0 |
2.1 |
2.9 |
4.0 |
[A1]/[B] |
2.4 |
2.1 |
2.4 |
2.0 |
2.4 |
1.1 |
1.7 |
1.4 |
2.0 |
0.9 |
2.9 |
4.0 |
[Table 2]
|
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Example 10 |
Example 11 |
Example 12 |
Evaluation results |
KV100 |
mm2/s |
6.8 |
6.7 |
6.8 |
6.8 |
6.7 |
6.6 |
6.9 |
6.9 |
6.6 |
6.6 |
6.7 |
6.9 |
HTHS 150 |
MPa·s |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.4 |
2.4 |
CCS viscosity |
Pa·s |
3.2 |
3.1 |
3.4 |
3.3 |
3.3 |
3.4 |
3.4 |
3.4 |
3.1 |
3.0 |
3.1 |
3.2 |
Torque reduction ratio |
% |
5.99 |
7.71 |
8.04 |
6.40 |
7.40 |
7.43 |
7.45 |
8.66 |
7.50 |
7.29 |
7.40 |
6.90 |
Diameter of shell wear scar |
mm |
0.64 |
0.63 |
0.68 |
0.55 |
0.62 |
0.61 |
0.66 |
0.66 |
0.63 |
0.52 |
0.61 |
0.61 |
Hot tube |
270°C |
7.5 |
7.5 |
6.5 |
5.5 |
5.5 |
8.5 |
5.5 |
5.5 |
7.5 |
6.0 |
5.5 |
8.0 |
[CCS viscosity]/[B] |
|
0.0046 |
0.0044 |
0.0049 |
0.0047 |
0.0047 |
0.0034 |
0.0034 |
0.0034 |
0.0044 |
0.0043 |
0.0044 |
0.0046 |
[Table 3]
|
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
Comparative Example 4 |
Comparative Example 5 |
Comparative Example 6 |
Comparative Example 7 |
Comparative Example 8 |
Lubricant base oil |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
balance |
(A1-1) magnesium salicylate ([Mg], ppm by weight) |
0 |
0 |
0 |
300 |
600 |
1,900 |
0 |
0 |
(A2-1) magnesium sulfonate ([Mg], ppm by weight) |
0 |
0 |
0 |
0 |
0 |
0 |
600 |
0 |
(A1-2) calcium salicylate 1 ([Ca], ppm by weight) |
1,900 |
1,900 |
1,900 |
1,400 |
900 |
0 |
0 |
0 |
(A1-3) calcium salicylate 2 ([Ca], ppm by weight) |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
(A2-2) calcium sulfonate ([Ca], ppm by weight) |
0 |
0 |
0 |
0 |
0 |
0 |
900 |
1,700 |
[A1] total ([Ca] + [Mg]) |
1,900 |
1,900 |
1,900 |
1,700 |
1,500 |
1,900 |
0 |
0 |
[A1]]/[A] (% by weight) |
100 |
100 |
100 |
100 |
100 |
100 |
0 |
0 |
(B) molybdenum-based friction modifier |
700 |
1,000 |
1,000 |
300 |
300 |
700 |
700 |
700 |
Anti-wear agent 1 |
1 |
1 |
- |
1 |
1 |
1 |
1 |
1 |
Anti-wear agent 2 |
- |
- |
1 |
- |
- |
- |
- |
- |
Antioxidant |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
Ash-free dispersant |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
3.6 |
Viscosity index improver |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
8.7 |
Anti-foaming agent |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0-1 |
[A]/[B] |
2.7 |
1.9 |
1.9 |
5-7 |
5.0 |
2-7 |
2-1 |
2.4 |
[A1]/[B] |
2-7 |
1.9 |
1.9 |
5.7 |
5.0 |
2.7 |
0.0 |
0.0 |
[Table 4]
|
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
Comparative Example 4 |
Comparative Example 5 |
Comparative Example 6 |
Comparative Example 7 |
Comparative Example 8 |
Evaluation results |
KV100 |
mm2/s |
6.8 |
6.9 |
6.9 |
6.7 |
6.8 |
6.8 |
6.4 |
6.5 |
HTHS 150 |
MPa·s |
2.3 |
2.3 |
2.3 |
2.3 |
2.3 |
2.4 |
2.3 |
2.3 |
CCS viscosity |
Pa·s |
3.2 |
3.4 |
3.4 |
3.3 |
3.3 |
3.2 |
3.0 |
3.0 |
Torque reduction ratio |
% |
0.86 |
2.91 |
5.30 |
1.70 |
3.40 |
6.00 |
4.50 |
4.20 |
Diameter of shell wear scar |
mm |
0.53 |
0.63 |
0.61 |
0.54 |
0.62 |
0.81 |
0.63 |
0.60 |
Hot tube |
270°C |
6.5 |
6.5 |
4.0 |
3.0 |
4.0 |
9.0 |
1.0 |
1.0 |
[CCS viscosity]/[B] |
|
0.0046 |
0.0034 |
0.0034 |
0.0110 |
0.0110 |
0.0046 |
0.0043 |
0.0043 |
[0093] As indicated in Table 4, the compositions of Comparative Examples 1 to 3 in which
the content of calcium salicylate (A1) was high had a low torque reduction ratio,
and the composition of Comparative Example 6 containing a large amount of magnesium
salicylate (A) caused a large wear. Further, the compositions of Comparative Examples
4 and 5 in which the amount of the molybdenum-based friction modifier (B) was less
than the lower limit of the present invention had a low torque reduction ratio and
exhibited poor high-temperature detergency. Moreover, the compositions of Comparative
Examples 7 and 8 which did not contain any metal salicylate not only had a low torque
reduction ratio but also exhibited poor high-temperature detergency.
[0094] On the other hand, as indicated in Table 2, the lubricant compositions according
to the present invention caused only a small wear and exhibited a high torque reduction
ratio and excellent high-temperature detergency, despite having a low kinematic viscosity
at 100°C.