Field of Invention
[0002] The present invention relates to an excellent fuel-efficient, low-viscosity lubricating
oil composition for an automobile engine, and in particular, relates to a lubricating
oil composition for automobile engine lubrication that, while being an excellent fuel-efficient,
low-viscosity lubricating oil composition for engine lubrication, also shows high
wear resistance. The present invention relates to a low-viscosity lubricating oil
composition that is particularly suitable for lubricating a motorcycle four-cycle
gasoline engine or a diesel engine having an exhaust gas after-treatment device.
Background of Invention
[0003] There is an increasing demand for improved fuel efficiency in automobiles. Therefore,
there is a need for an excellent fuel-efficient, low-viscosity engine oil as the lubricating
oil composition (engine oil) that is used to lubricate the engine of a gasoline engine
vehicle or a diesel engine vehicle. For instance, engine oils that have an SAE viscosity
grade of 5W20 and a high-temperature high-shear viscosity (value measured at 150°C
when the shear velocity or shear rate is 10
6 s
-1) of 2.6 mPa·s are already being used for practical purposes as fuel-efficient lubricating
oil compositions for gasoline engines in four-wheel drive vehicles.
[0004] However, by means of four-cycle gasoline engines for motorcycles, the engine oil
is also used to lubricate the transmission system and there is a chance that wear
of the energy-transmission devices, such as the transmission gears, will increase
(wear resistance will decrease) as a result of a reduction in viscosity of the engine
oil. Taking this point into consideration, JASO T903-2006 stipulates that the engine
oils for motorcycle four-cycle gasoline engines have a high-temperature, high-shear
(10
6s
-1) viscosity of 2.9 mPa·s or greater. Nevertheless, such a high high-temperature, high-shear
viscosity can hardly been expected of the SAE5W20 engine oils known today and therefore,
the engine oils used today in motorcycle four-cycle gasoline engines are all low-viscosity
engine oils of SAEI viscosity grade 10W30, 5W30, or 0W30.
[0005] On the other hand, taking into consideration the need for wear resistance in engine
oils, ACEA C1-08 and C2-08, which are the European standards for engine oils appropriate
for lubrication of diesel engine vehicles having diesel particulate filters, set the
lower limit of high-temperature, high-shear (10
6s
-1) viscosity of engine oils at 2.9 mPa·s and, in order to limit evaporation loss of
engine oils, the upper limit of NOACK evaporation loss at 13%.
[0006] Patent Document
JP (Kokai) 6-306384 describes a fuel-efficient lubricating oil for an internal combustion engine wherein
a predetermined amount of an organic molybdenum compound is added to a mineral oil
base oil having a dynamic viscosity at 100°C of 3 to 5 cSt, a viscosity index of 135
or higher, and a paraffin to total carbon ratio (%Cp) of 90% or higher.
[0007] Patent Document
JP (Kohyo) 2003-505533 describes a lubricating oil composition that, as a molybdenum additive-free, fuel-efficient,
low-volatility lubricating oil composition having a NOACK volatility of 15 wt% or
less, contains a predetermined amount of a calcium detergent and a predetermined amount
of an oil-soluble organic wear-improving agent, as well as a base oil comprising at
least 50 wt% of mineral oil; has a dynamic viscosity at 100°C of 4.0 to 5.5 mm
2/s; contains 95 wt% or more of saturated product and 25 wt% or less of naphthenes;
has a viscosity index of at least 120; and has an NOACK volatility of 15.5 wt% or
less.
[0008] Patent Document
JP (Kokai) 2000-87070 describes an excellent fuel-efficient motorcycle four-cycle engine composition having
an oil consumption-lowering effect that contains a hydrocarbon lubricating oil base
oil having a dynamic viscosity at 100°C of 3 to 10 mm
2/s and a viscosity index of 120 or higher, or a mixed base oil containing at least
15 mass% of this base oil, a zinc dialkyl dithiophosphate, a metal detergent, an ash-free
dispersant, a wear regulator, and a viscosity index-improving agent that brings dynamic
viscosity at 100°C of this composition to 9.3 to 16.5 mm
2/s. Specifically, it describes a motorcycle four-cycle engine composition having an
SAE viscosity grade of 10W30 or 10W40.
Summary of Invention
[0009] Improving engine structure is of course important as a method for improving fuel
efficiency of automobile engines, but it is also known that lowering viscosity of
lubricating oils is effective in improving fuel efficiency. Therefore, as previously
mentioned, engine oils having an SAE viscosity grade of 5W20 and a high-temperature,
high-shear (10
6s
-1) viscosity of 2.6 mPa·s are already being used as fuel-efficient gasoline engine
oils for four-wheel drive vehicles. Nevertheless, fuel-efficient gasoline engine oils
for four-wheel drive vehicles having an SAE viscosity grade of 5W20 cannot be expected
to have a high-temperature, high-shear viscosity that is as high as 2.6 mPa·s and
therefore, there is a problem in that when used as the engine oil of a motorcycle
four-cycle gasoline engine that uses engine oil for lubrication of the transmission
system, there is a problem in that wear resistance is insufficient.
[0010] The inventors completed the present invention upon discovering that it is possible
to produce a lubricating oil composition that has an SAE viscosity grade of 5W20 and
yet a viscosity index within a range of 140 to 230, a high-shear (10
6s
-1) viscosity at 150°C of 2.9 mPa·s or higher, a NOACK evaporation loss of 13% or less,
and excellent wear resistance by using a base oil such as has been recently supplied
to the market and is primarily isoparaffin, has an ultrahigh viscosity index wherein
the viscosity index is within a range of approximately 133 to 160, and is obtained
by hydrogenation and isomerization of a slack wax or a synthetic wax produced by the
Fischer-Tropsch method and distillation and dewaxing treatment, and by optimizing
the combination of additive components added to the base oil and the amount of each
lubricant component. Note that lubricating oil compositions of SAE viscosity grade
5W20 are already known to have excellent fuel efficiency because they have a relatively
low dynamic viscosity under temperature conditions of both low temperatures and high
temperatures.
[0011] Consequently, the present invention is a lubricating oil composition for automobile
engine lubrication, which is a lubricating oil composition comprising a base oil and
the following additive components and having an SAE viscosity grade of 5W20, wherein
the viscosity index is within a range of 140 to 230, the high-shear viscosity at 150°C
is 2.9 mPa·s or higher, and the NOACK evaporation loss is 13% or less, further comprising:
- a) a nitrogen-containing ash-free dispersant at 0.01 to 0.3 mass% in terms of the
nitrogen content,
- b) an alkaline earth metal-containing detergent at 0.08 to 0.4 mass% in terms of alkaline
earth metal content,
- c) a phosphorus-containing anti-wear agent at 0.05 to 0.12 wt% in terms of phosphorus
content,
- d) an antioxidant selected from the group consisting of amine compounds, phenol compounds,
and molybdenum compounds at 0.1 to 7 mass%,
- e) a viscosity index-improving agent at 0.5 to 20 mass%, and further wherein
the amount of each additive component is the mass% in terms of the total amount of
lubricating oil composition.
[0012] It should be noted that the phrase "lubricating oil composition having an SAE viscosity
grade of 5W20 of the present invention" refers to a lubricating oil composition that
satisfies the viscosity property of "5 W20" described in "SAE viscosity grades for
engine oils" of the American Petroleum Institute (revised in 2007). Moreover, the
phrase "high-shear viscosity" refers to the measured value (shear viscosity) when
the shear speed or shear rate is 10
6s
-1.
[0013] The present invention also is a method for lubricating a motorcycle four-cycle gasoline
engine or a diesel engine having an exhaust gas after-treatment device.
Detailed Description of the Invention
[0014] The lubricating oil composition for lubricating an automobile engine provided by
the present invention is a lubricating oil composition having an SAE viscosity grade
that is low at 5W20, while having a high-temperature, high-shear viscosity of 2.9
mPa·s or higher, and shows excellent fuel efficiency and wear resistance. The lubricating
oil compositor of the present invention therefore is an excellent fuel-efficient,
wear-resistant lubricating oil that is particularly suitable for lubricating a motorcycle
four-cycle gasoline engine or a diesel engine having an exhaust gas after-treatment
device.
[0015] The following are preferred modes of the lubricating oil composition for lubricating
an automobile engine of the present invention.
- (1) Dynamic viscosity at 100°C is within a range of 8.5 mm2/s or greater, but less than 9.3 mm2/s.
- (2) The base oil comprises as a base oil component at least 80 mass% of a mineral
oil base oil having a dynamic viscosity at 100°C that is within a range of 2 to 9
mm2/s (particularly preferably 4.5 to 9 mm2/s, further preferably 5 to 8.5 mm2/s) and a viscosity index of 133 to 160.
- (3) The base oil is a mineral oil having a dynamic viscosity at 100°C that is within
a range of 2 to 9 mm2/s (particularly preferably 4.5 to 9 mm2/s, further preferably 5 to 8.5 mm2/s) and a viscosity index of 133 to 160.
- (4) The base oil is a base oil having a viscosity index of 133 to 160 that is obtained
by hydrogenation and isomerization of either a slack wax or a synthetic wax produced
by the Fischer-Tropsch method and then distillation and dewaxing treatment.
- (5) The lubricating oil comprises two or more base oil components having different
viscosities, but both having a viscosity index of 130 or higher.
- (6) The viscosity index-improving agent is a polymethacrylate polymer having a shear
stability index (SSI, as defined by ASTM D6022) of 30 or less.
- (7) An organic sulfur compound is further added as an additive component.
- (8) The nitrogen-containing ash-free dispersant is a succinimide compound having a
bis structure.
- (9) The alkaline earth metal-containing component is a perbasic calcium-containing
compound selected from the group consisting of perbasic calcium sulfonate and perbasic
calcium phenate.
- (10) The phosphorus-containing anti-wear agent is a phosphorus-containing compound
selected from zinc dihydrocarbyl dithiophosphate and zinc dihydrocarbyl phosphate.
- (11) The viscosity index-improving agent is a polymethacrylate viscosity index-improving
agent.
- (12) The lubricating oil composition is for lubrication of a motorcycle four-cycle
gasoline engine.
- (13) The lubricating oil composition is for lubricating the engine of a diesel engine
vehicle having an exhaust gas post-purification device.
[0016] The base oil and additive components that are contained in the lubricating oil composition
of the present invention will now be described.
Base oil
[0017] Taking into consideration economics, the base oil of the lubricating oil composition
of the present invention is preferably a mineral oil. It can also be a mixture of
a relatively large amount (at least 50 mass%) of a mineral oil and a relatively small
amount (less than 50 mass%) of a synthetic oil.
[0018] Preferably the base oil used in the lubricating oil composition of the present invention
is a base oil that is primarily an isoparaffin and has a dynamic viscosity at 100°C
of 2 to 9 mm
2/s, a saturated component content of 95 mass% or higher (particularly 98 mass% or
higher), and a viscosity index of 133 or higher (particularly 135 or higher, further
145 or higher). A base oil having such properties and composition can be used alone,
or a combination of two or more types can be used. Moreover, it is also possible to
use a mixture of a base oil having such properties and composition and a relatively
small amount of a base oil having other properties and composition. Preferably the
base oil composition after mixing will still have the above-mentioned properties and
composition.
[0019] The base oil having the above-mentioned properties and composition preferably has
an evaporation loss (ASTM D5800) of 16% or less (particularly 15% or less, further
13% or less). When evaporation loss of the base oil is high, oil consumption with
long-term use of an engine oil that uses this base oil (lubricating oil composition)
under high temperatures increases, and the rise in viscosity increases. This leads
to a reduction in fuel efficiency.
[0020] There are no particular restrictions to the type of base oil showing the above-mentioned
properties and composition, but when the base oil is a mineral oil, preferably it
is a high-viscosity index base oil (base oil having a viscosity index between 133
and 160) the primary component of which is isoparaffin obtained by subjecting the
slack wax that is the by-product of dewaxing during the production of mineral oil
lubricating base oils, or synthetic wax synthesized using natural gas as the starting
material (by the Fischer-Tropsche method), to hydrogenation and isomerization and
then distillation and dewaxing. Such a high viscosity index base oil has a relatively
high dynamic viscosity at 100°C, but has good low-temperature viscosity properties
and therefore, can have a reduced evaporation loss and is ideal as the base oil of
the lubricating oil composition of the present invention.
[0021] It should be noted that, as described above, the high-viscosity-index base oil, which
is the above-mentioned mineral oil, can be used together with a synthetic oil. Preferably
the synthetic oil has the above-mentioned properties and composition. The preferred
synthetic oil can be selected from a variety of conventional synthetic oils, and examples
of such synthetic oils are various esters, alkylbenzenes, and polyalphaolefins (PAO).
Poly-alphaolefins (PAOs) are particularly preferred.
Nitrogen-containing ash-free dispersant
[0022] The lubricating oil composition of the present invention comprises a nitrogen-containing
ash-free dispersant (component a) in an amount within a range of 0.01 to 0.3 mass%
in terms of the nitrogen content. Preferably the mass-average molecular weight of
the nitrogen-containing ash-free dispersant is within a range of 4,500 to 20,000.
The phrase "mass-average molecular weight" used in the present specification is the
molecular weight determined by GPC analysis with polystyrene as the standard substance.
[0023] Typical examples of the nitrogen-containing ash-free dispersant used in the lubricating
oil composition of the present invention are alkenyl and alkyl succinimides derived
from polyolefins and derivatives of these succinimides. The amount added is within
a range of 0.01 to 0.3 mass% in terms of the nitrogen content based on the total mass
of the lubricating oil composition. Typical succinimides are obtained by reacting
a succinic anhydride substituted by alkenyl or alkyl groups and having a high molecular
weight and a polyalkylene polyamine containing an average of four to ten (preferably
five to seven) nitrogen atoms per molecule. The succinimide anhydride that is substituted
by alkenyl or alkyl groups and has a high molecular weight is preferably a polyolefin
having a number-average molecular weight of approximately 900 to 5,000, particularly
polybutene.
[0024] In many cases, chlorination by chlorine is used during the step for obtaining a polybutenyl
succinimide by reacting polybutene and maleic anhydride. However, although reactivity
is good by this method, it has the effect of a large amount of chlorine (for instance,
approximately 2,000 ppm) remaining in the succinimide final product. On the other
hand, when thermal reaction that does not use chlorine is employed, the residual chlorine
contained in the final product can be kept to a very low level (for instance, 30 ppm
or less). Moreover, when polybutene (at least approximately 50% of which is a methylvinylidene
structure) having a high reactivity in comparison to conventional polybutene (that
is primarily β-olefin in structure) is used, there is an advantage in that reactivity
is increased, even by the thermal reaction method. The amount of unreacted polybutene
in the dispersant decreases as the reactivity increases and therefore, it is possible
to obtain a dispersant having a high effective component (succinimide) concentration.
Consequently, preferably the succinimide that is used is produced by obtaining a polybutenyl
succinimide anhydride by thermal reaction using highly reactive polybutene and then
reacting this polybutenyl succinic anhydride with a polyalkylene polyamine having
an average of four to ten nitrogen atoms (per one molecule). This succinimide can
be further reacted with boric acid or an alcohol, aldehyde, ketone, alkyl phenol,
cyclic carbonate, organic acid, and the like and used as a so-called modified succinimide.
In particular, a boric acid-containing alkenyl (or alkyl) succinimide obtained by
reaction with boric acid or a boron compound can be used in order to efficiently increase
thermal and oxidation stability. Examples of this succinimide are mono-types, bis-types,
and poly-types in accordance with the number of imide structures per molecule, but
the bis-type or poly-type is preferred as the succinimide used for the purpose of
the present invention.
[0025] Examples of other nitrogen-containing ash-free dispersants are polymeric succinimide
dispersants derived from ethylene-α-olefin copolymer (having a molecular weight of
1,000 to 15,000, for instance) and alkenyl benzylamine ash-free dispersants.
[0026] According to the lubricating oil composition of the present invention, Nitrogen-containing
dispersion-type viscosity index improvers can also be used in place of the nitrogen-containing
ash-free dispersant. A nitrogen-containing olefin polymer or a nitrogen-containing
polymethacrylate having a mass-average molecular weight of 90,000 or greater (in terms
of polystyrene molecular weight by GPC analysis) is used as the nitrogen-containing
dispersion-type viscosity index-improving agent. Taking thermal stability into consideration,
the former nitrogen-containing olefin copolymer is effective.
[0027] The lubricating oil composition of the present invention contains a nitrogen-containing
ash-free dispersant and/or nitrogen-containing dispersion-type viscosity index-improving
agent as an active ingredient. These can also be used in combination with another
ash-free dispersant, such as an alkenyl succinic acid ester ash-free dispersant.
Metal-containing detergent
[0028] The lubricating oil composition of the present invention contains, as a metal-containing
detergent, an alkaline earth metal-containing detergent (component (b)) in an amount
within a range of 0.08 to 0.4 mass%. Examples of alkaline earth metals are calcium,
barium, and magnesium, but calcium is preferred. Moreover, preferably a sulfonate
or phenate of the alkaline earth metal is used as the metal-containing detergent.
A combination of a sulfonate of an alkaline earth metal and a phenate of an alkaline
earth metal can also be used. It is also possible to use a combination of these metal-containing
detergents and a metal-containing detergent such as an alkyl salicylate and/or alkyl
carboxylate of an alkaline earth metal (particularly calcium).
[0029] Examples of calcium sulfonates are perbasic calcium sulfonate having a total base
value of 150 to 500 mgKOH/g and low-basic calcium sulfonate having a total base value
of 5 to 60 mgKOH/g. Preferably the perbasic calcium sulfonate is perbasic alkylated
calcium benzene sulfonate or alkylated calcium toluene sulfonate having alkyl groups
with 10 or more carbon atoms (usually the degree of perbasic conversion is within
a range of 5 to 25). On the other hand, preferably the low-basic calcium sulfonate
is alkylated calcium benzene sulfonate or alkylated calcium toluene sulfonate having
alkyl groups with ten or more carbon atoms and is usually one that is nearly a neutral
salt subjected to virtually no perbasic conversion (preferably the degree of perbasic
conversion is within a range of 0.1 to 1.5). However, preferably a combination of
a perbasic calcium sulfonate and a low-basic calcium sulfonate is used. It should
be noted that the sulfonate can be a synthetic sulfonate as described above, or it
can be a petroleum sulfonate obtained by sulfonating a lubricating oil fraction of
a mineral oil to a calcium salt. Consequently, a petroleum low-basic calcium sulfonate/perbasic
calcium sulfonate such as described above is preferred for the purpose of the present
invention.
[0030] Perbasic sulfurized calcium phenate having a total base value of 120 to 350 mgKOH/g
is known as a calcium phenate. A perbasic sulfurized alkyl phenol calcium having alkyl
groups with ten or more carbon atoms is preferred.
Phosphorus-containing anti-wear agent
[0031] The lubricating oil composition of the present invention contains a phosphorus-containing
anti-wear agent (component c) in an amount within a range of 0.05 to 0.12 mass% in
terms of the amount of phosphorus. Preferred phosphorus-containing anti-wear agents
are zinc dihydrocarbyl dithiophosphate, zinc dihydrocarbyl monothiophate, and zinc
dihydrocarbyl phosphate, which are known as lubricating oil additives that are multiperformance
in that they have antioxidant performance and anti-wear performance.
[0032] A primary or secondary alkyl group-type zinc dialkyl dithiophosphate is usually used
as the zinc dihydrocarbyl dithiophosphate. A zinc dialkyl dithiophosphate having secondary
alkyl groups derived from a C
3-18 secondary alcohol is effective in terms of anti-wear performance. In contrast to
this, a zinc dialkyl dithiophosphate having primary alkyl groups derived from a C
3-18 primary alcohol has a tendency toward being superior in terms of heat resistance
and wear-reducing activity. Moreover, a combination of a secondary alkyl group-type
zinc dialkyl dithiophosphate and a primary alkyl group-type zinc dialkyl dithiophosphate
can be used. Furthermore, it is also possible to use a zinc dialkyl dithiophosphate
that is a mixed type of primary and secondary alkyl groups derived from a mixed alcohol
of a primary alcohol and a secondary alcohol.
[0033] A zinc dialkylaryl dithiophosphate (such as a zinc dialkylaryl dithiophosphate derived
from dodecyl phenol) can also be used as the phosphorus-containing anti-wear agent.
[0034] Moreover, it is also possible to use a phosphoric acid ester, phosphorus acid ester,
or thiophosphoric acid ester as the phosphorus-containing anti-wear agent.
Anti-oxidant
[0035] The lubricating oil composition of the present invention further contains, in an
amount that is within a range of 0.1 to 7 mass%, at least one antioxidant (component
d) selected from the group consisting of phenol compounds (phenol antioxidants), amine
compounds (amine antioxidants), and molybdenum compounds (molybdenum antioxidants).
[0036] A hindered phenol compound is generally used as the phenol antioxidant, and a diaryl
amine compound is generally used as the amine antioxidant. Hindered phenol antioxidants
and diaryl amine antioxidants are both also effective in improving high-temperature
detergency. Diaryl amine antioxidants in particular have a base value derived from
nitrogen and are effective in improving high-temperature detergency. On the other
hand, hindered phenol antioxidants are effective in preventing oxidative degradation
by NO
x.
[0037] Examples of hindered phenol antioxidants are 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol),
4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isoropylidenebis(2,6)\-di-t-butylphenol),
4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol),
2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and octyl 3-(5-t-butyl-4-hydroxy-3-methylphenyl)propionate.
[0038] Examples of amine antioxidants are C
4-9 mixed alkyl diphenyl amines, p,p'-dioctyldiphenylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine,
alkylated-α-naphthylamine, and alkylated-phenyl-α-naphthylamine.
[0039] Examples of molybdenum antioxidants are oxymolybdenum complexes of basic nitrogen
compounds. Examples of preferred oxymolybdenum complexes of basic nitrogen compounds
are oxymolybdenum complexes of succinimide and oxymolybdenum complexes of carbonamide.
Oxymolybdenum complexes of basic nitrogen compounds can be produced using the following
method, for instance. A molybdenum complex is produced by reacting an acidic molybdenum
compound or salt thereof with a basic nitrogen compound, such as a succinimide, carbonamide,
hydrocarbon monoamine, hydrocarbon polyamine, Mannich hydrochloric acid, phosphonamide,
thiophosphonamide, phosphoric amide, dispersion-type viscosity index-improving agent
(or a mixture thereof), while maintaining the reaction temperature at 120°C or lower.
[0040] Moreover, it is also possible to use a molybdenum-containing compound other than
an oxymolybdenum complex of a basic nitrogen compound in place of the oxymolybdenum
complex of the basic nitrogen compound, or in combination with the oxymolybdenum complex
of a basic nitrogen compound. Examples of the combined molybdenum-containing compounds
that can be used are sulfurized oxymolybdenum dithiocarbamates and sulfurized oxymolybdenum
dithiophosphates.
[0041] The phenol antioxidant (particularly hindered phenol antioxidant), amine antioxidant
(particularly diaryl amine antioxidant), and molybdenum antioxidant (particularly
oxymolybdenum complex of basic nitrogen compound) can be used alone, or they can be
used as an arbitrary combination with one another as desired. It is also possible
to use these in combination with an oil-soluble antioxidant.
Viscosity index-improving agent
[0042] The lubricating oil composition of the present invention further comprises a viscosity
index-improving agent (component e) in an amount within a range of 0.5 to 20 mass%.
Examples of viscosity index-improving agents are polymethacrylate viscosity index-improving
agents such as polyalkylmethacrylate, and viscosity index-improving agents based on
olefin copolymers, such as ethylene-propylene copolymer, styrene-butadiene copolymer,
and polyisoprene. Of these viscosity index-improving agents, olefin copolymer viscosity
index-improving agents have high thermal stability and are effective in terms of the
object of the present invention. One having a shear stability index (SSI) of 30 or
less (particularly 25 or less) is particularly preferable for the object of the present
invention. Moreover, a dispersion-type viscosity index-improving agent or multifunctional
viscosity index-improving agent that imparts dispersion performance to these polymer
compounds is preferably used. These viscosity index-improving agents can be used alone,
or a combination of any two or more viscosity index-improving agents can be used.
Organic sulfur compound
[0043] Preferably the lubricating oil composition of the present invention further comprises
an organic sulfur compound that is effective in terms of wear resistance and oxidation
resistance. Examples of organic sulfur compounds having such a property are sulfurized
olefins, sulfurized esters, sulfurized oils and fats, polysulfide compound, dimercaptothiadiazoles,
dithiophosphoric acid esters, and dithiocarbamates.
Other additives
[0044] The addition of an alkali metal borate hydrate to the lubricating oil composition
of the present invention is effective in terms of high-temperature detergency and
imparting a base value. The amount of alkali metal borate hydrate is 5 mass% or less,
particularly 0.01 to 5 mass%. Alkali metal borate hydrates often have an ash component,
sulfur component, and the like, but taking into consideration the properties of the
lubricating oil composition of the present invention, an alkali metal borate hydrate
can be effectively used by adjusting the amount added.
[0045] The lubricating oil composition of the present invention can also contain a small
amount of various auxiliary additives. Examples of such auxiliary additives are zinc
dithiocarbamate and methylene bis(dibutyl dithiocarbamate), oil-soluble copper compounds,
and organic amide compounds (such as oleyl amide) that function as antioxidants or
anti-wear agents. Moreover, it is possible to add compounds such as benzotriazole
compounds and thiadiazole compounds that function as metal deactivators. It is possible
to add polyoxyalkylene nonionic surfactants such as polyoxyethylene alkylphenyl ethers
and copolymers of ethylene oxide and propylene oxide that function as anti-rust agents
and demulsifiers. It is possible to add various amides, polyhydric alcohol aliphatic
acid esters, or derivatives thereof that function as wear adjusters. Moreover, it
is possible to add a variety of compounds that function as antifoaming agent and pour
point depressants. Note that preferably these auxiliary additives are each used in
an amount that is 3 mass% or less (particularly a range of 0.001 to 3 mass%) in terms
of the lubricating oil composition.
Examples
[0046] The present invention is further described by the following illustrative non-limiting
working examples.
[Examples 1 and 2, comparative examples, and reference examples]
(1) Production of lubricating oil composition
[0047] The lubricating oil composition of the present invention (SAE viscosity grade: 5W20,
high-temperature, high-shear viscosity: 2.9 mPa·s or higher) was produced (Examples
1 and 2) using the following base oil and additives (in the following amounts). Moreover,
a lubricating oil composition having an SAE viscosity grade of 5W20 (high-temperature,
high-shear viscosity of approximately 2.6 mPa·s) was produced as a comparative example
and a lubricating oil composition having an SAE viscosity grade of 10W30 (high-temperature,
high-shear viscosity of 2.9 mPa·s or higher) was produced as a reference example.
(2) Base oil
[0048] Base oill: Mixture (having viscosity index of 142, a dynamic viscosity at 100°C of
4.9 mm
2/s, and NOACK evaporation loss of 10.1 %) of mineral oil base oil a (having a viscosity
index of 137, a dynamic viscosity at 100°C of 4.1 mm
2/s, and a NOACK evaporation loss of 13.6%) obtained by hydrogenation and isomerization,
fractionation, and then dewaxing using slack wax as the starting material and mineral
oil base oil b (having a viscosity index of 148, a dynamic viscosity at 100°C of 6.6
mm
2/s, and NOACK evaporation loss of 5.0%) obtained by hydrogenation and isomerization,
fractionation, and then dewaxing using slack wax as the starting material, at a weight
ratio of 60:40 (base oil a:base oil b).
[0049] Base oil 2: Hydrocracked mineral oil (having a viscosity index of 128, a dynamic
viscosity at 100°C of 4.2 mm
2/s, and NOACK evaporation loss of 14.2%)
[0050] Base oil 3: Mixture (having viscosity index of 115, dynamic viscosity at 100°C of
6.7 mm
2/s, and NOACK evaporation loss of 10.8%) of hydrocracked mineral oil a (having a viscosity
index of 122, a dynamic viscosity at 100°C of 5.6 mm
2/s, and NOACK evaporation loss of 12.4%) and hydrocracked mineral oil b (having a
viscosity index of 99, a dynamic viscosity at 100°C of 10.7 mm
2/s, and NOACK evaporation loss of 6.0%), at a weight ratio of 73:27 (mineral oil a:mineral
oil b)
[0051] Note: The amount of base oil that, together with the total amount of the following
additives, brought the total to 100 mass%.
(3) Additives
[Nitrogen-containing ash-free dispersant]
[0052] 1) Ash-free dispersant 1 (mass-average molecular weight: 5,100 (in terms of polystyrene
by GPC analysis; same hereafter), nitrogen content: 1.95 mass%, boron content: 0.63
mass%, chlorine content: less than 5 ppm by mass; obtained by reacting a highly reactive
polyisobutene having a number-average molecular weight of approximately 1,300 (at
least approximately 50% of which had a methyl vinylidene structure) and maleic anhydride
by thermal reaction, reacting the resulting polyisobutenyl succinic anhydride with
a polyalkylene polyamine having an average number of nitrogen atoms of 6.5 (per one
molecule) to obtain the bis-type of succinimide, and then reacting this bis-type of
succinimide with boric acid)
Amount added: 0.06 mass% (in terms ofN)
[0053] 2) ash-free dispersant 2 (mass-average molecular weight: 12,800, nitrogen content:
1.0 mass%, chlorine content: 30 ppm by mass; obtained by reacting a highly reactive
polyisobutene having a number-average molecular weight of approximately 2,300 (at
least approximately 50% of which had a methyl vinylidene structure) and maleic anhydride
by thermal reaction, reacting the resulting polyisobutenyl succinic anhydride with
a polyalkylene polyamine having an average number of nitrogen atoms of 6.5 (per one
molecule) to obtain the bis-type of succinimide, and then reacting this bis-type of
succinimide with ethylene carbonate)
Amount added: 0.01 mass% (in terms ofN)
[Alkaline earth metal-containing detergent]
[0054] 1) Perbasic calcium phenate (sulfurized phenate having C
12 branched alkyl groups, Ca: 9.6 mass%, S: 3.4 mass%, TBN: 264 mgKOH/g)
Amount added: 0.15 mass% (in terms of Ca)
[0055] 2) Perbasic calcium sulfonate (alkyl toluene sulfonate having C
20-24 alkyl groups, Ca: 16.0 mass%, S: 1.6 mass%, TBN: 425 mgKOH/g, degree of perbasic
conversion: 19)
Amount added: 0.07 mass% (in terms of Ca)
[0056] 3) Low-basic calcium sulfonate (alkyl benzene sulfonate having C
14-24 alkyl groups, Ca: 2.4 mass%, S: 2.9 mass%, TBN: 17 mgKOH/g, degree of perbasic conversion:
0.34)
Amount added: 0.01 mass% (in terms of Ca)
[Zinc dithiophosphate]
[0057] Zinc di(secondary-alkyl) dithiophosphate (P: 7.2 mass%< Zn: 7.8 mass%, S: 14 mass%,
produced derived from C
3-8 secondary alcohol)
Amount added: 0.06 mass% (in terms of P)
[0058] Zinc di(primary alkyl) dithiophosphate (P: 7.3 mass%, Zn: 8.4 mass%, S: 14 mass%,
produced derived from C
8 primary alcohol)
Amount added: 0.03 mass% (in terms of P)
[Antioxidant]
[0059] Dialkyl diphenyl amine (alkyl groups: mixture of C
4 and C
8, N: 4.6 mass) Amount added: 0.45 mass%
[Organic sulfur compound] (used in Example 2 only)
[0060] Sulfurized isobutylene (S: 42 mass%)
[0061] Amount added: 0.3 mass%
[Viscosity index-improving agent]
[0062] Polymethacrylate viscosity index-improving agent (SSI = 18, mass-average molecular
weight: 200,000) - used in examples 1 and 2 and comparative example
[0063] Amount added: 5.1 mass% (example 1), 5.0 mass% (example 2), 5.1 mass%
(Comparative example)
[0064] Ethylene propylene copolymer viscosity index-improving agent (SSI = 24) - used in
Reference example
[0065] Amount added: 4.6 mass%
[Pour point depressant]
[0066] Polymethacrylate pour point depressant: 0.3 mass%
[Other additives]
[0067] Combination of small amounts each of additives such as anti-wear agent, anti-rust
agent, defoaming agent, and the like
[0068] Amount added: 0.6 mass%
Evaluation of lubricating oil composition
[0069]
(1) Viscosity properties of lubricating oil composition (high-temperature, high-shear
viscosity, dynamic viscosity (at 100°C and 40°C), viscosity index, cranking viscosity
(at -25°C or -30°C) and pumping temperature (at -35°C) were determined under the conditions
described below.
(2) Moreover, the NOACK evaporation loss (%) at 250°C of the lubricating oil composition
was determined by ASTM D5800, method B.
(3) Furthermore, the Shell four spheres test was conducted as a test to evaluate wear
resistance. According to the Shell four spheres test, sample oil was heated to 75°C
and tests were performed for 60 minutes under a load of 40 kgf at 1,200 rotations
per minute. The diameter of the abrasion scar left on the surface of the test spheres
was determined.
Table 1 shows the properties of each of the lubricating oil compositions and the results
of the Shell four spheres test of examples 1 and 2, the comparative example, and the
reference example.
Table 1
|
|
Example 1 |
Example 2 |
Comparative Example |
Reference Example |
Viscosity grade |
5W20 |
5W20 |
5W20 |
10W30 |
Base oil |
Base oil 1 |
Base oil 1 |
Base oil 2 |
Base oil 3 |
High-temperature, high-shear viscosity |
2.93 |
2.91 |
2.62 |
3.15 |
Dynamic viscosity (100°C) |
9.15 |
9.05 |
8.02 |
10.1 |
Dynamic viscosity (40°C) |
44.1 |
43.7 |
36.3 |
65.7 |
Viscosity index |
196 |
195 |
203 |
139 |
Cranking viscosity |
- |
- |
- |
5815 |
|
-25°C |
|
|
|
|
|
-30°C |
3630 |
3590 |
2800 |
- |
Pumping viscosity at -35°C |
Passed |
Passed |
Passed |
Passed* |
NOACK evaporation loss (%) |
9.7 |
9.8 |
14.0 |
11.5 |
Shell four spheres test |
0.47 |
0.47 |
0.54 |
0.48 |
|
Average abrasion diameter (mm) |
|
|
|
|
[0070] Note: The high-temperature, high-shear viscosity is the viscosity at a shear speed
of 10
6s
-1 and temperature of 150°C (units mPa·s). The dynamic viscosity units are mm
2/s and the cranking viscosity units are mPa·s. Moreover, a pumping viscosity that
"passed" means that the pumping viscosity satisfied the regulation for pumping viscosity
(at a determination temperature of -35°C) for SAE viscosity grade 5W20. However, the
determination temperature was -30°C for pumping viscosity required by 10W30 and the
"passed*" indicates that the determination passed the regulation for pumping viscosity
at -30°C.
[0071] The following are clear from the properties and results of evaluating each lubricating
oil composition of examples 1 and 2, the comparative example, and the reference example
shown in Table 1.
- (1) The lubricating oil composition of examples 1 and 2 is an excellent fuel-efficient
SAE grade 5W20 lubricating oil composition, but has virtually the same wear resistance
as the SAE grade 10W30 lubricating oil composition of the reference example, which
is of relatively inferior fuel efficiency.
- (2) On the other hand, the lubricating oil composition of the comparative example
has a high NOACK evaporation loss, low high-temperature, high-shear viscosity, and
inferior wear resistance.