[0001] This invention relates to engine oil compositions, and more particularly to engine
oil compositions which provide excellent fuel efficiency and viscosity at low temperatures
and are less in evaporation loss.
[0002] The fuel consumption reduction of automobile engines implemented since the oil crisis
is still one of the important issues from the view point of resource- and environment-protection.
The fuel consumption reduction of automobiles has been put into practice by reducing
the body weight of an automobile, improving combustion efficiency, and reducing the
occurrence of friction in an engine.
[0003] The reduction of fiction in engines has been implemented by improving the movable
valve structures, reducing the number of piston rings, smoothing the abrasive surfaces
of sliding parts, and using fuel efficient engine oils.
[0004] Among these measures for reducing fuel consumption, the use of such fuel efficient
engine oils has become general in the market because of their excellent balance of
cost and performances. The engine oils are blended with effective additives such as
friction modifiers. However, in order to make friction modifiers exhibit their performances
sufficiently, it is important to carefully select a base oil and formulate the other
engine oil additives.
[0005] Japanese Patent Laid-Open Publication No. 8302378 discloses an engine oil composition
which comprises a specific base oil, an alkaline earth metal salicylate-based detergent,
zinc dialkyldithiophosphate, a polybutenylsuccinimidebased ashless dispersant, a phenol-based
ashless oxidation inhibitor, a molybdenumdithiocarbamatebased friction modifier, a
viscosity index improves, in a specific amount, respectively.
[0006] Reducing the viscosity of an engine oil is considered to be one of the measure to
provide an engine oil with good fuel efficiency. However, no particular examination
or research has not sufficiently been done on a base oil or additives for a low viscosity
engine oil.
[0007] An object of the present invention is to provide an engine oil composition which
is reduced more in viscosity than conventional fuel efficient engine oils and provide
excellent fuel efficiency and viscosity characteristics at low temperatures with less
evaporation loss by blending suitable additives.
[0008] As a result of an extensive research and development, it was found that an engine
oil composition which is reduced more in viscosity than conventional fuel efficient
engine oils and provide excellent fuel efficiency and viscosity characteristics at
low temperatures and is less in evaporation loss can be obtained by blending a specific
base oil with an specific amount of a polymethacrylate-based viscosity index improver.
BRIEF SUMMARY OF THE PRESENT INVENTION
[0009] According to the present invention, there is provided an engine oil composition which
comprises (A) a lubricant base oil having a kinematic viscosity at 100 ° C of 2 to
6 mm
2/S, a viscosity index of 120 or more and a total aromatic content of 15 percent by
mass or less and (B) a polymethacrylate-based viscosity index improver blended in
such an amount that the composition has a kinematic viscosity at 100 ° C of 4.0 to
9.3 mm
2/s.
[0010] Furthermore, according to the present invention, there is provided an engine oil
composition which comprises (A) a lubricant base oil having a kinematic viscosity
at 100 ° C of 2 to 6 mm
2/S, a viscosity index of 120 or more and a total aromatics content of 15 percent by
mass or less; (B) a polymethacrylate-based viscosity index improver blended in such
an amount that the composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3
mm
2/s; and (C) molybdenumdithiocarbamate.
[0011] The polymethacrylate-based viscosity index improver have preferably have an weight-average
molecular weight of 180,000 or more.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
[0012] The present invention is described below in more detail.
[0013] A lubricating base oil referred to as Component (A) in an engine oil composition
according to the present invention has a kinematic viscosity at 100 ° C of which upper
limit is 6 mm
2/s, preferably 5 mm
2/s and lower limit is 2 mm
2/s, preferably 3 mm
2/s. Lubricant base oils in excess of the upper limit would lead to increased fluid
resistance resulting in increased loss caused by wear occurring at engine parts to
be lubricated, while those of less than the lower limit would lead to insufficient
oil-film formation, resulting in less lubricity and increased evaporation loss.
[0014] Component (A) has necessarily a viscosity index of 120 or more. Such a viscosity
index value is contributive to the production of an engine oil composition having
excellent low-temperature viscosity characteristics. Base oils having a viscosity
index of less than 120 would lead to a necessity to bring it down lower viscosity,
resulting in the increased evaporation loss and viscosity of the resulting engine
oil.
[0015] The upper limit of aromatic content of Component (A) is 15 percent by mass, preferably
10 percent by mass, and most preferably 5 percent by mass. Base oils in excess of
the upper limit would fail to achieve synergistic effects with each additive to be
used in the present invention. No particular limitation is imposed on the lower limit
of aromatic content. However, Component (A) has preferably a total aromatic content
of 2 percent by mass or more because that having a total aromatic content of less
than 2 percent by mass would not possibly exhibit solubility to various additives.
[0016] The term "total aromatic content" used herein denotes an aromatic fraction content
measured in accordance with ASTM D2549. Incorporated by the aromatic fraction are
generally alkylbenzenes, alkylnaphthalenes, anthracene, phenanthrene, alkylated products
thereof, compounds in which 4 or more benzene rings are condensed, and compounds having
hetero-aromatics, such as pyridines, quinolines, phenols, and naphthols.
[0017] Eligible base oils for the present invention are mineral lubricating oils, synthetic
lubricating oils, and mixtures of two or more of these oils mixed in a suitable ratio.
[0018] For instance, the base oils are exemplified by mineral lubricating oils, mixtures
of mineral lubricating oils and non-aromatic containing synthetic lubricating oils,
and mixtures of aromatic-containing synthetic lubricating oils and non-aromatics containing
synthetic lubricating oils.
[0019] The term "mineral lubricating oil" used herein denotes not only a single mineral
lubricating oil but also a mixture of two or more mineral lubricating oils. Therefore,
when using two more mineral lubricating oils as the base oil, there may be used not
only a mixture of mineral lubricating oils each having a total aromatic content of
15 percent by mass or less but also a mixture of a mineral lubricating oil having
a total aromatic content of 15 percent by mass and a mineral lubricating oil having
a total aromatic content exceeding 15 percent by mass as long as the resulting base
oil has a total aromatic content of 15 percent by mass or less.
[0020] Furthermore, when using a mixture of a mineral lubricating oil and a non-aromatic
containing synthetic lubricating oil, there may be used a mineral lubricating oil
having a total aromatic content exceeding 15 percent by mass as long as the resulting
base oil has a total aromatic content of 15 percent by mass or less.
[0021] Specific examples of the mineral lubricating oil are those obtained by subjecting
a lubricant fraction obtained by vacuum-distilling an atmospheric residue derived
from the atmospheric distillation of crude oil to one or more refining processes such
as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, and
hydrorefining.
[0022] Specific examples of the aromatic-containing synthetic lubricating oil are alkylnaphthalenes
and alkylbenzenes.
[0023] Specific examples of the non-aromatic containing synthetic lubricating oil are polybutens
and hydrides thereof; poly-α-olefins such as 1-octene oligomer and 1-decene oligomer,
and hydrides thereof; diesters such as ditridecylglutarate, di-2-ethylhexyladipate,
disodecyladipate, and di-2-ethylhexylcebacate; polyolesters such as trimethylolpropanecaprylate,
trimethylolpropanepelargonate, pentaerythritol-2-ehylhexyanoate, and pentaerythritolpelargonate;
and mixtures thereof.
[0024] Each of these lubricating oil exhibits its peculiar viscosity-temperature characteristics,
i.e., viscosity index. As long as a lubricating oil used as a base oil of the present
invention has a viscosity index of 120 or more, even though a lubricating base selected
from the above has a viscosity index of less than 120, it may be used in combination
with those having a viscosity index of 120 or more.
[0025] Component (B) of an engine oil composition according to the present invention is
a polymethacrylate-based viscosity index improver blended in such an amount that the
resulting composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3 mm
2/s. The kinematic viscosity at 100 ° C of the resulting composition in excess of 9.3
mm
2/S would not provide sufficient fuel efficiency, while that of less than 4.0 mm
2/s would improve fuel efficiency caused by the reduced viscosity of the composition
and viscosity at low temperatures but fail to have sufficient lubricity as an engine
oil.
[0026] The combination of a base oil with such a polymethacrylate-based viscosity index
improver in an engine oil composition according to the present invention results in
enhanced viscosity index improving effects, less thickening effects, and excellent
pour point reduction effects. The polymethacrylate-based viscosity index improver
is indispensable in an engine oil composition according to the present invention in
order to provide it with excellent low temperature characteristics.
[0027] Whereas, when using known polyoleinfin copolymer-based viscosity index improver,
the same effects as the present invention can not be achieved.
[0028] The polymethacrylate-based viscosity index improvers which may be used in the present
invention are any type of non-dispersion type or dispersion type polymethacrylate
compounds which are used as viscosity index improvers for a lubricating oil.
[0029] The non-dispersion type polymethacrylate-based viscosity index improver may be a
polymer of a compound represented by the formula

[0030] In formula (1), R
1 is a straight or branched alkyl group such as methyl, ethyl, propyl, butyl, hexyl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, and octadecyl groups.
[0031] Specific examples of the dispersion type polymethacrylate-based viscosity index improver
are copolymers obtained by copolymerizing one or more monomers selected from compounds
represented by formula (1) with one or more nitrogen-containing monomers selected
from compounds represented by formulae (2) and (3)

[0032] In formulae (2) and (3), R
2 and R
4 are each independently hydrogen or methyl. R
3 is a straight or branched alkylene group having 1 to 18 carbon atoms, such as ethylene,
propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,
undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene,
and octadecylene groups. e is an integer of 0 or 1. X1 and X2 are each independently
an amino- or heterocyclic- residue having 1 or 2 nitrogen and 0 to 2 oxygen. Specific
examples of X1 and X2 are dimethylamino, diethylamino, dipropylamino, dibutylamino,
anilino, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pyrolyl, pyridyl,
methylpydidyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino,
and pyrazino groups.
[0033] Specific examples of the nitrogen-containing monomer represented by formula (2) or
(3) are dimethylaminomethylmethacrylate, diethylaminomethylmethacrylate, dimethylaminoethylmethacrylate,
diethylaminoethylmethacrylate, 2-methyl-5-vinylpyridine, morpholinomethylmethacrylate,
morpholinoethylmethacrylate, N-vinylpyrrolidone, and mixtures thereof.
[0034] Regardless of how much weight-average molecular weight the polymethacrylate-based
viscosity index improver has, it can improve the low temperature viscosity characteristics.
However, the lower limit of the weight-average molecular weight of the polymethacrylate-based
viscosity index improver, which is effective in improving the performance of an engine
oil, is preferably 180,000, more preferably 190,000. Polymethacrylate-based viscosity
index improvers having a weight-average molecular weight of 180,000 or more can decrease
the amount of other viscosity index improvers to be added so as to further improve
low temperature viscosity, not only leading to an advantage in terms of cost but also
an improvement in shear stability such that the initial performances of the resulting
engine oil can be maintained. No particular limitation is imposed on the upper limit.
When consideration is given to an easy treatment of the composition, it is preferably
500,000 or less and more preferably 400,000 or less.
[0035] As described above, an engine oil composition according to the present invention
contains the polymethacrylate-based viscosity index improver in such an amount that
the composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3 mm
2/s. As long as the kinematic viscosity at 100 ° C of an engine oil composition is
within this range, the content of a polymethacrylate-based viscosity index improver
may be arbitrary selected. However, the content is preferably from 0.5 to 10 percent
by mass based on the total weight of the composition.
[0036] In order to further enhance fuel efficiency, an engine oil composition according
to the present invention may be blended with molybdenumdithiocarbamate represented
by formula (4) or mixtures thereof

[0037] In formula (4), R
5, R
6, R
7, and R
8 may be the same or different and are each independently an alkyl or alkylaryl group
having 2 to 18 carbon atoms. Y
1, Y
2, Y
3, and Y
4 are each independently sulfur or oxygen. The alkyl group includes primary, secondary,
and tertiary alkyl groups which may be straight or branched. Specific examples of
the alkyl group are ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and
tridecyl groups. Specific examples of the molybdenumdithiocarbamate are molybdenumdiethyldithiocarbamate
sulfide, molybudenumdipropyldithiocarbamate sulfide, molybdenumdibutyldithiocarbamate
sulfide, molybdenumdipentyldithiocarbamate sulfide, molybdenumdihexyldithiocarbamate
sulfide, molybdenumdioctyldithiocarbamate sulfide, molybdenumdidecyldithiocarbamate
sulfide, molybdenumdidodecyldithiocarbamate sulfide, molybdenumditridecyldithiocarbamate
sulfide, molybdenumdi(butylphenyl)dithiocarbamate sulfide, molybdenumdi(nonylphenyl)dithiocarbamate
sulfide, oxymolybdenumdiethyldithiocarbamate sulfide, oxymolybdenumdipropyldithiocarbamate
sulfide, oxymolybdenumdibutyldithiocarbamate sulfide, oxymolybdenumdipentyldithiocarbamate
sulfide, oxymolybdenumdihexyldithiocarbamate sulfide, oxymolybdenumdioctyldithiocarbamate
sulfide, oxymolybdenumdidecyldithiocarbamate sulfide, oxymolybdenumdidodecyldithiocarbamate
sulfide, oxymolybdenumditridecyldithiocarbamate sulfide, oxymolybdenumdi(butylphenyl)dithiocarbamate
sulfide, and oxymolybdenumdi(nonylphenyl)dithiocarbamate sulfide. Mixtures of these
compounds may also be used.
[0038] The upper limit molybdenum content is 0.15 percent by mass, preferably 0.10 percent
by mass, in terms of molybdenum concentration, based on the total mass of the composition.
The content in excess of the upper limit would cause the formation of sludge when
the engine oil is deteriorated. No particular limitation is imposed on the lower limit
molybdenum content. However, the lower limit is preferably 0.02 percent by mass, more
preferably 0.04 percent by mass in terms of molybdenum concentration, based on the
total mass of the composition in order to obtain a sufficient friction reduction effect.
[0039] As described above, an engine oil composition according to the present invention
excels in fuel efficiency and low temperature viscosity and is less in evaporation
loss by blending a specific base oil with a polymethacrylate-based viscosity index
improver so as to obtain a specific viscosity. Furthermore, the use of a polymethacrylate-based
viscosity index improver having a weight average molecular weight of 180,000 or more
can further improve fuel efficiency and low temperature viscosity. Higher level of
fuel efficiency can be provided in an engine oil by adding thereto molybdenumdithiocarbamate.
[0040] For the purpose of enhancing these various performances and other various performances
required for an engine oil composition, known engine oil additives may be used singlely
or in combination.
[0041] Examples of such known additives which may be used in the present invention are alkaline
earth metal-based detergents, ashless dispersants, corrosion inhibitors, ashless oxidation
inhibitors, friction modifiers other than molybdenumdithiocarbamate, corrosion inhibitors,
demulsifying agents, metal deactivators, and antifoamers.
[0042] Eligible alkaline earth metal-based detergents are alkaline earth metal compounds
which are added in a lubricating oil. Specific examples of such a detergent are one
or more metallic detergents selected from alkaline earth metal sulfonates, alkaline
earth metal phenates, and alkaline earth metal salicylates.
[0043] Preferred alkaline earth metal sulfonates are alkaline earth metal salts, preferably
magnesium salt and/or calcium salt of an alkyl aromatic sulfonic acid obtained by
sulfonating an alkyl aromatic compound having a molecular weigh of 300 to 1,500, preferably
400 to 700. The latter is more preferred.
[0044] The above-mentioned alkyl aromatic sulfonic acid may be a petroleum sulfonic acid
and a synthetic sulfonic acid.
[0045] The petroleum sulfonic acid may be mahogany acid obtained by sulfonating the alkyl
aromatic compound contained in the lubricant fraction of mineral oil or by-produced
upon the production of white oil. The synthetic sulfonic acid may be those obtained
by sulfonating alkyl benzene having a straight or branched alkyl group, which may
be by-produced from a plant for producing alkyl benzene used as material of detergents,
or sulfonating dinonylnaphthalene. Although not restricted, there may be used fuming
sulfuric acid and sulfuric acid as a sulfonating agent.
[0046] The alkaline earth metal phenate may be an alkaline earth metal salt, preferably
magnesium salt and/or calcium salt of alkylphenol, alkylphenolsulfide, or a product
resulting from Mannich reaction of the alkylphenol. Specific examples are those represented
by the formulae

wherein R
9, R
10, R
11, R
12, R
13, and R
14 may be the same or different and are each independently a straight or branched alkyl
group having 4 to 30, preferably 6 to 18 carbon atoms, M
1, M
2, and M
3 are each independently an alkaline earth metal, preferably calcium and/or magnesium,
and x is an integer of 1 or 2.
[0047] Specific examples of R
9, R
10, R
11, R
12, R
13, and R
14 are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl,
docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,
and triacontyl groups, all of which may be straight or branched and primary, secondary
or tertiary alkyl groups.
[0048] The alkaline earth metal salicylate may be an alkaline earth metal salt, preferably
magnesium salt and/or calcium salt of an alkyl salicylate. Specific examples are those
represented by the formula

wherein R
15 is a straight or branched alkyl group having 4 to 30, preferably 6 to 18 carbon atoms,
and M
4 is an alkaline earth metal, preferably calcium and/or magnesium.
[0049] Specific examples of R
15 are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl,
docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,
and triacontyl groups, all of which may be straight or branched and primary, secondary
or tertiary alkyl groups.
[0050] Moreover, the alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline
earth metal salicylate may be a neutral alkaline earth metal sulfonate, alkaline earth
metal phenate and alkaline earth metal salicylate obtained by directly reacting a
compound such as the above-mentioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol
sulfide and the Mannich reaction product thereof, and alkyl salicylic acid with an
alkaline earth metal oxide or hydroxide of magnesium and/or calcium, or obtained by
converting the compound into an alkali metal salt such as sodium salt or potassium
salt and then substituting the alkali metal salt with an alkaline earth metal salt.
The alkaline earth metal sulfonate, alkaline earth metal phenate or alkaline earth
metal salicylate may also be a basic alkaline earth metal sulfonate, alkaline earth
metal phenate or alkaline earth metal salicylate obtained by heating a neutral alkaline
earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate
in water containing an excess amount of an alkaline earth metal salt or an alkaline
earth metal base; or an overbased alkaline earth metal sulfonate, alkaline earth metal
phenate or alkaline earth metal salicylate obtained by reacting a neutral alkaline
earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate
with the carbonic acid salt or boric acid salt of an alkaline earth metal in the presence
of carbon dioxide.
[0051] In the present invention, there may be used the above-described neutral alkaline
earth metal salt, basic alkaline earth metal salt, overbased alkaline earth metal
salt, and mixtures thereof.
[0052] Commercially available metallic detergents are usually diluted with a light lubricating
base oil. It is preferred to use metallic detergents containing metal in an amount
of 1.0 to 20 percent by mass, preferably 2.0 to 16 percent by mass.
[0053] No particular limitation is imposed on the total base number of the alkaline earth
metal detergent used in the present invention. However, preferred metallic detergents
are those having a total base number of 30 to 400 mgKOH/g, preferably 150 to 300 mgKOH/g.
The term "total base number" used herein denotes a total base number measured by the
perchloric acid potentiometric titration method in accordance with section 7 of JIS
K2501 "Petroleum products and lubricants-Determination of neutralization number"
[0054] Although not restricted, the content of the alkaline earth metal detergent is within
the range of 1.0 to 10.0 percent by mass, preferably 1.0 to 8.0 percent by mass, more
preferably 1.5 to 5.0 percent by mass, based on the total mass of the composition.
[0055] Preferred ashless dispersant are any type of polybutenylsuccinimides used in a lubricating
oil. Specific examples of such dispersants are mono-type imides represented by formula
(9), bis-type imides represented by formula (10), and those modified with organic
acid or boric acid

[0056] In formulae (9) and (10), R
16, R
17, and R
18 are each independently a polybutenyl group having a number-average molecular weight
of 900 to 3,500, preferably 1,000 to 3,000, and c is an integer of 2 to 5.
[0057] No particular limitation is imposed on a method for producing the polybutenylsuccinimides.
For instance, the polybutenylsuccinimides may be obtained by reacting polybutenylsuccinate
resulting from the reaction of a polybutene or chlorinated polybutene having a number-average
molecular weight of 900 to 3,500, with maleic anhydride. Specific examples of the
polyamine are diethyltriamine, triethylenetetraamine, tetraethylenepentamine, and
pentaethylenehexamine.
[0058] The upper limit content of the polybutenylsuccinimide is 0.20 percent by mass, preferably
0.10 percent by mass, in terms of nitrogen concentration, based on the total mass
of the composition. Contents in excess of the upper limit would adversely affect rubber-made
sealing materials of an engine. No particular limitation is imposed on the lower limit
content of the polybutenylsuccinimide. However, the lower limit is preferably 0.05
percent by mass, more preferably 0.06 percent by mass, in terms of nitrogen concentration,
based on the total mass of the composition such that a more sufficient fuel efficiency
can be achieved.
[0059] Alternatively, an engine oil composition may be blended with one or more of other
ashless dispersants such as a long chain polyalkylamine, and an amide of a long chain
fatty acid and a polyamine or with those in combination with the above-described polybutenylsuccinimide
ashless dispersant.
[0060] Wear inhibitors used in the present invention may be one or more dialkyldithio zinc
phosphate selected from compounds represented by formula (11)

[0061] In formula (11), R
19, R
20, R
21, and R
22 are each independently a primary alkyl group having 2 to 18, preferably 4 to 12 carbon
atoms or a secondary alkyl group having 3 to 18, preferably 3 to 10 carbon atoms.
[0062] The primary alkyl group having 2 to 18 carbon atoms are those represented by the
formula

[0063] In formula (12), R
23 is a straight or branched alkyl group having 1 to 17, preferably 3 to 11 carbon atoms.
Specific examples of R
23 are straight or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, and heptadecyl groups.
[0064] The secondary alkyl group having 3 to 18 carbon atoms are those represented by the
formula

[0065] In formula (13), R
24 and R
25 are each independently a straight or branched alkyl group having 1 to 16, preferably
1 to 8 carbon atoms to be selected such that the total carbon number of R
24 and R
25 is 2 to 17, preferably 2 to 9 carbon atoms. Specific examples of R
24 and R
25 are straight or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
and hexadecyl groups.
[0066] The upper limit content of the dialkyldithio zinc phosphate is 0.10 percent by mass,
preferably 0.09 percent by mass, on an elementary basis, based on the total mass of
the composition. The content in excess of the upper limit would accelerate the poisoning
of a ternary catalyst adversely affecting exhaust gas. No particular limitation is
imposed on the lower limit content of the dialkyldithio zinc phosphate. In order to
maintain the friction coefficient after the deterioration of an engine oil, lower
i.e., to maintain fuel efficiency longer, the lower limit is preferably 0.04 percent
by mass, more preferably 0.06 percent by mass, on an elementary basis, based on the
total mass of the composition.
[0067] An engine oil composition may be blended with one or more of other friction modifies
such as organic phosphates, fatty acids, fatty acid esters, aliphatic alcohols, or
with those in combination with the above-described dialkyldithio zinc phosphates.
[0068] Preferred ashless oxidation inhibitors are phenolic ashless oxidation inhibitors
used as oxidation inhibitors for a lubricating oil. Specific examples of the phenolic
ashless oxidation inhibitors are 4,4'-methylenebis(2,6-di-tertbutylphenol), 4,4'-bis(2,6-di-tert-butylphenol),
4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol),
2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol),
4,4'-isopropylidenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol),
2,2'-isobutylidenebis(4,6-dimethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol,
2,6-di-tert-butyl-4(N,N'-dimethylamino-p-cresol, 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol),
4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol),
2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide,
bis(3,5-ditert-butyl-4-hydroxybenzyl)sulfide, 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
tridecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetraquis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
octadecyl-3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, and mixtures thereof.
[0069] An engine oil composition may be blended with one or more of the above-described
ashless dispersants or with one or more of amine-based ashless dispersants such as
phenyl-α-nephtylamine, alkylphenyl-a-nephtylamine, and dialkyldiphenylamine. Alternatively,
the above-described phenolic ashless dispersants may be sued in combination with the
amine-based ashless dispersants.
[0070] The upper limit content of the above-described ashless oxidation inhibitors is 3.0
percent by mass, preferably 2.0 percent by mass. A content in excess of the upper
limit would fail to achieve oxidation inhibition that balances the amount. No particular
limitation is imposed on the lower limit content. However, the lower limit content
of preferably 0.1 percent by mass, more preferably 0.3 percent by mass is contributive
to reduce the friction coefficient of an engine oil after being deteriorated.
[0071] An engine oil composition according to the present invention may be blended with
friction modifiers other than the above-described molybdenumdithiocarbamates. Such
friction modifiers may be molybdenumdithiophosphate, molybdenum disulfide, long-chain
aliphatic amines, long-chain fatty acids, long-chain fatty acid esters, long-chain
aliphatic alcohols.
[0072] Additives other than those of the above-described which may be used in the present
invention are corrosion inhibitors such as petroleum sulfonates, alkylbenzene sulfonates,
dinonylnaphthalene sulfonates, alkenylsuccinates, and polyalcohol esters; demulsifying
agent, typical examples of which are polyalkylene glycol-based non-ionic surfactants
such as polyoxyethylenealkyl ether, polyoxyethylenealkylphneyl ether, and polyoxyethylenealkylnaphthyl
ether; metal diactivators such as imidazoline, pyrimidine derivatives, alkylthiadiazole,
mercaptobenzothizole, benzotriazole and derivatives thereof, 1,3,4-thiadiazolepolysulfide,
1,3,4-thiadizolyl-2,5-bisdialkyldithiocarbamte, 2-(alkyldithio)benzoimidazole, and
β-(o-carboxybenzylthio)propionnitrile; and antifoamers such as slicone, fluorosilicone,
and fluoroalkyl ether.
[0073] When adding these additive to an engine oil composition according to the present
invention, the corrosion inhibitors and demulsifying agents are each added in an amount
of 0.1 to 15 percent by mass, the antifoamers are added in an amount of 0.0005 to
1 percent by mass, and the metal deactivators are added in an amount of 0.005 to 1
percent by mass, based on the total mass of the composition.
[0074] An engine oil composition according to the present invention may be used preferably
in motorcycle engines, automobile engines, diesel engines for land use, and marine
diesel engines.
[0075] The invention will be further described by way of the following examples which are
provided for illustrative purposes only. The performances of engine oils used in inventive
examples and comparative examples were evaluated by the following performance evaluating
tests.
(1) Engine motoring test
[0076] The friction torque of the whole of an engine was measured by driving at 1,500 rpm,
at an oil temperature of 80 ° C, and at a water temperature of 80 ° C. In general,
an engine oil has better fuel efficiency with the smaller value which indicates the
smaller friction loss at each parts of the engine.
(2) NOACK evaporation test (ASTM D 5880)
[0077] The evaporation loss of each of the engine oils was measured after being heated at
a temperature of 250 ° C and under a constant pressure for one hour. An engine oil
with the smaller value is less consumed during actual running.
(3) CCS viscosity (ASTM D 5293)
[0078] This test evaluates the cranking performance of each of the engine oils. Engine oils
with the smaller value has better low temperature viscosity characteristics.
Inventive Examples 1-3
[0079] Table 1 shows the above performance evaluation test results of the engine oils of
Inventive Examples 1 - 3. Each of the engine oils was formulated so as to have the
same kinematic viscosity at 100 ° C and high temperature high shear viscosity at 150
° C. It is apparent from the results in Table 1 that the engine oils of Inventive
Examples 1 - 3 had an excellent fuel efficiency, less evaporation loss, and an excellent
low temperature viscosity. It was also apparent that these oils exhibited more excellent
performances when being blended with a polymethacrylate-based viscosity index improver
with a weight-average molecular weight of 250,000 than when being blended with that
of a weight-average molecular weight of 150,000. Furthermore, it was apparent that
the engine oils blend with molybdenumdithiocarbamate exhibited an excellent fuel efficiency.
Comparative Examples 1 - 3
[0080] Table 1 also shows the above performance evaluation test results of the engine oils
of Comparative Examples 1 - 3. The engine oil of Comparative Example 1 with the base
oil having a viscosity index of 100 was inferior in fuel efficiency, evaporation loss,
and low temperature viscosity. The engine oil containing an olefin copolymer-based
viscosity index improver (Comparative Examples 2) was inferior in fuel efficiency,
evaporation loss, and low temperature viscosity. The engine oil of Comparative Example
3 with a kinematic viscosity of 9.3 or more was inferior in fuel efficiency even though
being blended with molybdenumdithiocarbamate.
Table 1
| |
Inventive Example 1 |
Inventive Example 2 |
Inventive Example 3 |
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
| Base oil I1) Mass % |
85.9 |
85.9 |
84.3 |
|
79.7 |
82.3 |
| Base oil II2) mass % |
|
|
|
|
4.2 |
|
| Base oil III3) mass % |
|
|
|
85.9 |
|
|
| Viscosity index improver I4) mass % |
4.0 |
|
|
|
|
|
| Viscosity index improver II5) mass % |
|
4.0 |
4.0 |
4.0 |
|
6.0 |
| Viscosity index improver III6) mass % |
|
|
|
|
6.0 |
|
| MoDTC7) mass % |
|
|
1.6 |
|
|
1.6 |
| Additive Package 8) mass % |
10.1 |
10.1 |
10.1 |
10.1 |
10.1 |
10.1 |
| Kinematic viscosity (100°C) mm2/s |
8.25 |
8.33 |
8.32 |
8.39 |
8.24 |
9.45 |
| High temperature high shear Viscosity (150°C) mPa·s |
2.62 |
2.63 |
2.61 |
2.62 |
2.61 |
2.75 |
| Engine motoring friction torque Test N·m |
(○) 19.6 |
(○) 19.4 |
( ⓞ) 18.1 |
(x) 20.2 |
(x) 20.2 |
(x) 20.1 |
| NOACK Evaporation Mass % |
(○) 14 14 14 |
(○) 14 14 |
(○) 14 22 |
(x) 22 17 |
(x) 17 14 |
(○) 14 |
| CCS viscosity (-25°C) mPa·s |
(○) 3250 |
(○) 3200 |
(○) 3270 |
(x) 4630 |
(x) 4960 |
(○) 3300 |
1) hydrocracking mineral oil :
4.2 mm2/s of kinematic viscosity at 100° C, 3.1 mass % of total aromatics content, 125 of
viscosity index
2) hydrocracking mineral oil :
2.6 mm2/s of kinematic viscosity at 100° C, 2.1 mass % of total aromatics content, 104 of
viscosity index
3) solvent-refined mineral oil :
4.5 mm2/s of kinematic viscosity at 100° C, 25.3 mass % of total aromatics content, 100 of
viscosity index
4) Polymethacrylate-based viscosity index improver:
150,000 of weight-average molecular weight
5) Polymethacrylate-based viscosity index improver:
250,000 of weight-average molecular weight
6) Olefin copolymer-based viscosity index improver:
250,000 of weight-average molecular weight
7) Molybdenumdithiocarbamate represented by the formula

wherein R is an alkyl group having 8 or 13 carbon atoms, Y is Oxygen or sulfur,
4.8 mass % of molybdenum concentration
8) Additive mixtures containing calcium sulfonate, calcium salicylate, dialkyldithio
zinc phospahte, succinimide-based ashless dispersant, phenol-based oxidation inhibitor,
antifoamer, and corrosion inhibitor
[0081] As described above, the present invention can provide an engine oil composition which
excels in fuel efficiency and low temperature characteristics and encounters less
evaporation loss.