U.S. patent application number 14/904496 was filed with the patent office on 2016-06-02 for lubricant oil composition for internal combustion engine.
This patent application is currently assigned to JX NIPPON OIL & ENERGY CORPORATION. The applicant listed for this patent is JX NIPPON OIL & ENERGY CORPORATION. Invention is credited to Shintaro KUSUHARA, Hiroya MIYAMOTO.
Application Number | 20160152920 14/904496 |
Document ID | / |
Family ID | 52468361 |
Filed Date | 2016-06-02 |
United States Patent
Application |
20160152920 |
Kind Code |
A1 |
MIYAMOTO; Hiroya ; et
al. |
June 2, 2016 |
LUBRICANT OIL COMPOSITION FOR INTERNAL COMBUSTION ENGINE
Abstract
A lubricant oil composition for internal combustion engines with
which further reduction of friction can be achieved to provide
excellent fuel efficiency is provided. (A) A lubricant oil base oil
having a kinematic viscosity at 100.degree. C. of 2.0 to 5.0
mm.sup.2/s; (B) a molybdenum-based friction modifier in an amount
of 0.005 to 0.2 mass % in terms of the mass of the molybdenum
relative to the total mass of the composition; (C) a metal-based
detergent in an amount of 0.01 to 1 mass % in terms of the mass of
the metal relative to the total mass of the composition; and (D)
0.01 to 10 mass % of at least one compound selected from amino
acids having a C.sub.6-24 alkyl, alkenyl, or acyl group, and/or
derivatives of the amino acids.
Inventors: |
MIYAMOTO; Hiroya; (n/a,
IL) ; KUSUHARA; Shintaro; (Yokohama, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JX NIPPON OIL & ENERGY CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
JX NIPPON OIL & ENERGY
CORPORATION
Tokyo
JP
|
Family ID: |
52468361 |
Appl. No.: |
14/904496 |
Filed: |
August 13, 2014 |
PCT Filed: |
August 13, 2014 |
PCT NO: |
PCT/JP2014/071388 |
371 Date: |
January 12, 2016 |
Current U.S.
Class: |
508/365 |
Current CPC
Class: |
C10M 135/18 20130101;
C10N 2040/25 20130101; C10M 2215/08 20130101; C10M 169/04 20130101;
C10M 2215/042 20130101; C10M 2203/1025 20130101; C10M 133/18
20130101; C10M 2229/041 20130101; C10N 2010/12 20130101; C10M
163/00 20130101; C10N 2020/04 20130101; C10M 2215/102 20130101;
C10M 137/10 20130101; C10N 2030/06 20130101; C10N 2030/54 20200501;
C10N 2020/02 20130101; C10M 169/045 20130101; C10M 2215/28
20130101; C10M 2207/125 20130101; C10M 129/54 20130101; C10M
2223/045 20130101; C10M 2207/262 20130101; C10M 2209/084 20130101;
C10M 2215/04 20130101; C10M 2207/289 20130101; C10N 2030/52
20200501; C10M 101/02 20130101; C10N 2040/252 20200501; C10M
2219/068 20130101; C10N 2040/255 20200501; C10M 2215/082 20130101;
C10M 2203/1025 20130101; C10N 2020/02 20130101; C10M 2207/262
20130101; C10N 2010/04 20130101; C10N 2060/14 20130101; C10M
2203/1025 20130101; C10N 2020/02 20130101; C10M 2207/262 20130101;
C10N 2010/04 20130101; C10N 2060/14 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10M 129/54 20060101 C10M129/54; C10M 137/10 20060101
C10M137/10; C10M 133/18 20060101 C10M133/18; C10M 101/02 20060101
C10M101/02; C10M 135/18 20060101 C10M135/18 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 16, 2013 |
JP |
2013-169118 |
Claims
1. A lubricant oil composition for internal combustion engines, the
lubricant oil composition comprising: (A) a lubricant oil base oil
having a kinematic viscosity at 100.degree. C. of 2.0 to 5.0
mm.sup.2/s; (B) a molybdenum-based friction modifier in an amount
of 0.005 to 0.2 mass % in terms of the mass of the molybdenum
relative to the total mass of the composition; (C) a metal-based
detergent in an amount of 0.01 to 1 mass % in terms of the mass of
the metal relative to the total mass of the composition; and (D)
0.01 to 10 mass % of at least one compound selected from amino
acids having a C.sub.6-24 alkyl, alkenyl, or acyl group, and/or
derivatives of the amino acids.
2. The lubricant oil composition for internal combustion engines
according to claim 1, wherein the (C) metal-based detergent
contains at least a salicylate-based detergent.
3. The lubricant oil composition for internal combustion engines
according to claim 1, wherein the lubricant oil composition has a
kinematic viscosity at 100.degree. C. of 4.0 to 12.5
mm.sup.2/s.
4. The lubricant oil composition for internal combustion engines
according to claim 1, further comprising zinc dialkyl
dithiophosphate (ZnDTP) in an amount of 0.02 to 0.2 mass % in terms
of the mass of the phosphorus relative to the total mass of the
composition.
5. The lubricant oil composition for internal combustion engines
according to claim 2, wherein the lubricant oil composition has a
kinematic viscosity at 100.degree. C. of 4.0 to 12.5
mm.sup.2/s.
6. The lubricant oil composition for internal combustion engines
according to claim 2, further comprising zinc dialkyl
dithiophosphate (ZnDTP) in an amount of 0.02 to 0.2 mass % in terms
of the mass of the phosphorus relative to the total mass of the
composition.
7. The lubricant oil composition for internal combustion engines
according to claim 3, further comprising zinc dialkyl
dithiophosphate (ZnDTP) in an amount of 0.02 to 0.2 mass % in terms
of the mass of the phosphorus relative to the total mass of the
composition.
8. The lubricant oil composition for internal combustion engines
according to claim 5, further comprising zinc dialkyl
dithiophosphate (ZnDTP) in an amount of 0.02 to 0.2 mass % in terms
of the mass of the phosphorus relative to the total mass of the
composition.
Description
TECHNICAL FIELD
[0001] The present invention relates to a fuel-efficient lubricant
oil composition for internal combustion engines.
BACKGROUND ART
[0002] The trend for improving the fuel efficiency of automobiles
since the wake of the oil crisis remains an important issue in
light of resource protection and environmental protection, and the
need for improved fuel efficiency has been higher. The conventional
approach for improving the fuel efficiency of automobiles includes
vehicle weight reduction, improvement of engine combustion, and
reduction of friction in engines and the drive train. Low engine
friction is achieved through improving the valve train mechanism,
reducing the surface roughness of sliding members, and using a
fuel-efficient lubricant oil composition for internal combustion
engines (engine oil).
[0003] Among them, the use of a fuel-efficient engine oil is
gaining the acceptance in the market because of its high cost
effectiveness. As an effort to achieve high fuel efficiency through
engine oil, there have been studies of low-viscosity oils directed
to reducing a frictional loss under fluid lubricating conditions of
components such as pistons and bearing portions. There is also
proposed adding a friction modifier such as an organic molybdenum
compound to reduce a frictional loss in the mixed or boundary
lubrication of components such as the valve train.
[0004] Various such fuel-efficient engine oils have been proposed.
For example, PTL 1 proposes an engine oil composition in which
specific additives (e.g., an alkali earth metal salicylate-based
detergent, and a molybdenum dithiocarbamate-based friction
modifier) are added in specific amounts in a base oil having a
kinematic viscosity at 100.degree. C. of 2 to 8 mm.sup.2/s and
containing 15 mass % of aromatic. PTL 2 proposes a lubricant oil
composition for internal combustion engines in which a
molybdenum-based friction modifier or an ester- or amine-based
ashless friction modifier, and overbased Ca salicylate are mixed in
a lubricant oil base oil containing an ester-based lubricant oil
base oil having a kinematic viscosity at 100.degree. C. of 3 to 8
mm.sup.2/s. PTL 3 proposes a lubricant oil composition for internal
combustion engines in which oxymolybdenum dithiocarbamate sulfide
is combined with ashless friction modifiers such as acid amide
compounds, aliphatic partial ester compounds, and/or aliphatic
amine compounds.
[0005] However, a problem of the molybdenum-based friction modifier
is that increasing its content produces only a limited friction
reducing effect. There is also a stability problem due to formation
of precipitates. Another drawback is that use of the
molybdenum-based friction modifier with ester- or amine-based
ashless friction modifiers hardly improves the friction reducing
effect. In today's environment where the demand for more fuel
efficient lubricants continues to increase, the conventional engine
oils are insufficient in terms of fuel efficiency.
[0006] On the other hand, sarcosine and aspartic acid derivatives
are known examples of ashless friction modifiers (for example, PTL
4 to 6). However, adding of these modifiers in a lubricant oil
composition for internal combustion engines, and a synergistic
effect on reducing friction by using these modifiers with
molybdenum-based friction modifiers have not been known. Such an
effect also has not been anticipated by a skilled artisan.
CITATION LIST
Patent Literature
[0007] PTL 1: JP-A-8-302378
[0008] PTL 2: JP-A-2005-41998
[0009] PTL 3: JP-A-2008-106199
[0010] PTL 4: JP-A-9-316475
[0011] PTL 5: JP-A-2008-179669
[0012] PTL 6: JP-A-2005-290181
SUMMARY OF INVENTION
Technical Problem
[0013] The present invention is intended to provide a solution to
the foregoing problems, and it is an object of the present
invention to provide a lubricant oil composition for internal
combustion engines with which further reduction of friction can be
achieved to provide excellent fuel efficiency.
Solution to Problem
[0014] The present invention is a lubricant oil composition for
internal combustion engines, the lubricant oil composition
comprising:
[0015] (A) a lubricant oil base oil having a kinematic viscosity at
100.degree. C. of 2.0 to 5.0 mm.sup.2/s;
[0016] (B) a molybdenum-based friction modifier in an amount of
0.005 to 0.2 mass % in terms of the mass of the molybdenum relative
to the total mass of the composition;
[0017] (C) a metal-based detergent in an amount of 0.01 to 1 mass %
in terms of the mass of the metal relative to the total mass of the
composition; and
[0018] (D) 0.01 to 10 mass % of at least one compound selected from
amino acids having a C.sub.6-24 alkyl, alkenyl, or acyl group,
and/or derivatives of the amino acids.
[0019] It is preferable that the (C) metal-based detergent contains
at least a salicylate-based detergent. It is preferable that the
lubricant oil composition for internal combustion engines has a
kinematic viscosity at 100.degree. C. of 4.0 to 12.5 mm.sup.2/s. It
is preferable that the lubricant oil composition for internal
combustion engines further comprises zinc dialkyl dithiophosphate
(ZnDTP) in an amount of 0.02 to 0.2 mass % in terms of the mass of
the phosphorus relative to the total mass of the composition.
Advantageous Effects of Invention
[0020] The lubricant oil composition for internal combustion
engines of the present invention has notable effects, including low
frictional coefficient, and excellent fuel-efficient
performance.
DESCRIPTION OF EMBODIMENTS
(A) Lubricant Oil Base Oil
[0021] The lubricant oil base oil of the present invention is not
particularly limited, as long as it is a lubricant oil base oil
having a kinematic viscosity at 100.degree. C. of 2.0 to 5.0
mm.sup.2/s. Any lubricant oil base oil, regardless of mineral or
synthetic, which is used with a lubricant oil composition for
common internal combustion engines may be used.
[0022] The kinematic viscosity at 100.degree. C. of the lubricant
oil base oil is preferably 2.5 to 4.5 mm.sup.2/s, more preferably
3.0 mm.sup.2/s or more, further preferably 3.5 mm.sup.2/s or
more.
[0023] When the kinematic viscosity at 100.degree. C. is less than
2.0 mm.sup.2/s, oil film formation at lubricating portions becomes
insufficient, the lubricity suffers, and the evaporative loss of
the lubricant oil base oil increases. On the other hand, a
kinematic viscosity above 5. 0 mm.sup.2/s lowers the fuel-efficient
effect, and the viscosity characteristics at low temperature
deteriorate.
[0024] As used herein, "kinematic viscosity at 100.degree. C."
means a kinematic viscosity at 100.degree. C. as defined by ASTM
D-445 standards.
[0025] The lubricant oil base oil of the present invention has a
viscosity index of preferably 90 or more, more preferably 100 or
more. A viscosity index of abase oil below 90 increases the
low-temperature viscosity, and may cause poor starting performance.
As used herein, "viscosity index" means a viscosity index measured
according to JIS K2283-1993.
[0026] The lubricant oil base oil of the present invention may be a
mineral oil-based base oil or a synthetic base oil, or a mixture of
two or more mineral oil-based base oils, or a mixture of two or
more synthetic base oils, or may be a mixture of a mineral
oil-based base oil and a synthetic base oil, as long as the
foregoing physical properties for the lubricant oil base oil are
satisfied. The two or more base oils in the mixture may have any
desired mixture ratio.
[0027] The mineral oil-based base oil may be, for example, a
paraffin-based lubricant oil base oil or a naphthene-based
lubricant oil base oil obtained after a lubricant oil fraction from
the atmospheric distillation and vacuum distillation of crude oil
is purified by using an appropriate combination of purification
processes such as solvent deasphalting, solvent extraction,
hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining,
sulfuric acid treatment, and clay treatment.
[0028] Example of the synthetic base oil include
poly-.alpha.-olefins (for example, such as polybutene, 1-octene
oligomer, 1-decene oligomer, and ethylene-propylene oligomer) or
hydrides thereof, isobutene oligomers or hydrides thereof,
isoparaffin, alkylbenzene, alkylnaphthalene, diesters (for example,
such as dibutyl maleate, ditridecyl glutarate,
di-2-ethylhexyladipate, diisodecyladipate, ditridecyladipate, and
di-2-ethylhexylsebacate), copolymers of .alpha.-olefins and
diesters, polyolesters (for example, such as trimethylolpropane
caprylate, trimethylolpropane pelargonate,
pentaerythritol-2-ethylhexanoate, and pentaerythritol pelargonate),
dialkyl diphenyl ether, and polyphenyl ether.
[0029] When the lubricant oil base oil of the present invention is
a mineral oil-based base oil, the lubricant oil base oil has a
saturated hydrocarbon content of preferably 90% or more. As used
herein, "saturated hydrocarbon content" means a measured value
according to ASTM D-2007.
[0030] The base oil is preferably selected from those that fall
under group III or higher categories in the Base Stock Categories
of API (American Petroleum Institute), or from base oils obtained
through isomerization of waxes.
[0031] The producing process of the base oil is not particularly
limited. Preferably, the base oil is produced by desulfurization
and hydrocracking of an atmospheric residual oil obtained through
atmospheric distillation of crude oil, followed by fractionation of
the resulting oil into a set viscosity grade, or by solvent
dewaxing or catalytic dewaxing of the residual oil, and, as
required, solvent extraction and hydrogenation. Among them, the
base oil is preferably obtained through catalytic dewaxing.
[0032] In recent years, the lubricant oil base oil also includes
petroleum-based wax isomerized lubricant oil base oils, which are
produced by hydrogen isomerization of by-product petroleum-based
wax from a dewaxing process, wherein the dewaxing process is one
part of producing processes of a base oil including further vacuum
distillation of an atmospheric distillation residual oil and
fractionation into the desired viscosity grade, subsequent
processes such as solvent purification and hydrorefining, and
further subsequent solvent dewaxing; and also includes GTL-based
wax isomerized lubricant oil base oils produced through
isomerization of a GTL WAX (gas-to-liquid wax) produced by using
techniques such as the Fischer-Tropsch process. The producing
process of the wax isomerized lubricant oil base oil, in this case,
is basically the same as the producing process of the hydrocracked
base oil.
[0033] The % C.sub.A of the base oil is not particularly limited,
but is preferably less than 3, more preferably 2 or less, further
preferably 1 or less, most preferably substantially 0. With a %
C.sub.A above 10, improvement of heat resistance, one of the
objectives of the present invention, becomes insufficient.
[0034] Here, "% C.sub.A" is a value measured by using a method
(n-d-M ring analysis) according to ASTM D3238-85.
[0035] The sulfur content in the base oil is not particularly
limited, but is preferably 0.03 mass % or less, more preferably
0.01 mass % or less. Particularly preferably, the base oil is
substantially sulfur free. Lower sulfur contents mean higher
purity, and a less likelihood of causing the sludge solubility
problem.
[0036] The method used to measure sulfur content is not
particularly limited. Typically, for example, the JIS K2541-1996
method is used.
(B) Molybdenum-Based Friction Modifier
[0037] Examples of the molybdenum-based friction modifier of the
present invention include molybdenum dithiocarbamate (MoDTC) , and
molybdenum dithiophosphate (MoDTP) . Specific examples of the
molybdenum dithiocarbamate include the compounds represented by the
following general formula (1). Specific examples of the molybdenum
dithiophosphate include the compounds represented by the following
general formula (2).
##STR00001##
[0038] In general formulae (1) and (2), R.sup.1 to R.sup.8 each
independently represent C.sub.1-24 hydrocarbon groups, a, b, c, and
d each independently represent any one of integers of 0 to 4, which
satisfies a+b=4, and c+d=4.
[0039] Preferred examples of the C.sub.1-24 hydrocarbon groups
represented by R.sup.1 to R.sup.8 in general formulae (1) and (2)
each independently include linear or branched C.sub.1-24 alkyl
groups, C.sub.5-13 cycloalkyl groups or linear or branched
C.sub.5-13 alkylcycloalkyl groups, linear or branched C.sub.3-24
alkenyl groups, C.sub.6-18 aryl groups or linear or branched
C.sub.6-18 alkylaryl groups, and C.sub.7-19 arylalkyl groups. The
alkyl groups and the alkenyl groups may be primary, secondary, or
tertiary.
[0040] Other preferred examples of the molybdenum-based friction
modifier in the lubricant oil composition of the present invention
include organic molybdenum complexes as reaction products of basic
nitrogen compounds such as succinimide, acidic molybdenum compounds
such as molybdenum trioxide, and sulfur compounds such as hydrogen
sulfide and phosphorus pentasulfide.
[0041] The content of the molybdenum-based friction modifier in the
lubricant oil composition of the present invention is 0.005 mass %
to 0.2 mass o, preferably 0.01 mass % or more in terms of the mass
of the molybdenum element relative to the total mass of the
composition. A notable fuel-efficient effect cannot be obtained
when the content of the molybdenum-based friction modifier is less
than 0.005 mass % in terms of the mass of the molybdenum element.
On the other hand, with a molybdenum-based friction modifier
content exceeding 0.2 mass % in terms of the mass of the molybdenum
element, the extra content does not provide a proportional
improvement in the fuel-efficient effect. These contents should
thus be avoided.
[0042] The lubricant oil composition of the present invention can
preferably use molybdenum dithiophosphate and molybdenum
dithiocarbamate. However, it is particularly preferable to use
molybdenum dithiocarbamate because it can greatly improve the
fuel-efficient performance from low temperature to high temperature
in synergy with other components.
(C) Metal-Based Detergent
[0043] The metal-based detergent of the present invention may be
any of compounds commonly used for lubricants. For example,
overbased compounds of oil-soluble metal salts having a linear or
branched hydrocarbon group, and an OH group and/or a carbonyl group
may be used. It is also possible to use overbased metal salts such
as alkali earth metal sulfonate, alkali earth metal carboxylate,
alkali earth metal salicylate, alkali earth metal phenate, and
alkali earth metal phosphonate; and overbased metal salts obtained
through reaction of alkali earth metal hydroxide or oxide, and, as
required, boric acid or boric anhydride. Examples of the alkali
earth metal include magnesium, calcium, and barium, of which
calcium is preferred. More preferred for use as the overbased metal
salts are oil-soluble metal salts of OH group- and/or carbonyl
group-containing compounds overbased with alkali earth metal borate
or alkali earth metal carbonate. For fuel efficiency, it is
preferable to use alkali earth metal salicylate, more preferably
alkali earth metal salicylate overbased with alkali earth metal
borate.
[0044] The metal-based detergent of the present invention
preferably has a base number of 50 mgKOH/g or more, more preferably
100 mgKOH/g or more, further preferably 120 mgKOH/g or more,
particularly preferably 140 mgKOH/g or more. The base number is
preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or
less. With a base number of less than 50 mgKOH/g, the increased
viscosity decreases the fuel efficiency, and the friction reducing
effect from the addition of the metal-based detergent tends to
become insufficient. With a base number above 300 mgKOH/g, it tends
to inhibit the effects of other components such as an antiwear
additive, and the friction reducing effect tends to become
insufficient. As used herein, "base number" is a measured value
according to JIS K 2501 5.2.3.
[0045] The metal-based detergent used in the present invention may
be produced by using any method. For example, the metal-based
detergent can be obtained through reaction of the oil-soluble metal
salt, alkali earth metal hydroxide or oxide, and, as required,
boric acid or boric anhydride at 20 to 200.degree. C. for 2 to 8
hours in the presence of water, an alcohol (such as methanol,
ethanol, propanol, and butanol) , and a dilute solvent (such as
benzene, toluene, and xylene) , followed by heating at 100 to
200.degree. C., and removal of water, and, as required, the alcohol
and the dilute solvent. Specific reaction conditions are
appropriately selected according to such factors as the type of the
raw material, and the amount of the reactant. For details of the
producing process, see, for example, JP-A-60-116688, and
JP-A-61-204298. The oil-soluble metal salt overbased with alkali
earth metal borate produced as above has a total base number of
typically 100 mgKOH/g or more, and can preferably be used for the
lubricant oil composition of the present invention.
[0046] The metal-based detergent of the present invention has a
metal ratio of preferably 4.0 or less, more preferably 3.0 or less,
further preferably 2.0 or less. A metal ratio above 4.0 has the
possibility of reducing the friction torque, and specifically, the
fuel efficiency may become insufficient. The metal ratio of the
metal-based detergent is adjusted to preferably 1.0 or more, more
preferably 1.1 or more, further preferably 1.5 or more. With a
metal ratio of less than 1.0, the kinematic viscosity and the
low-temperature viscosity of the lubricant oil composition for
internal combustion engines increase, and may cause problems in
fuel efficiency or starting performance.
[0047] As used herein, "metal ratio" is represented by metallic
element valency.times.metallic element content (mol %)/soap group
content (mol %) in the metal-based detergent. The metallic element
includes calcium, and magnesium. The soap group includes a sulfonic
acid group, a phenol group, and a salicylic acid group.
[0048] The linear or branched hydrocarbon group of the metal-based
detergent of the present invention is preferably an alkyl group or
an alkenyl group. The alkyl or alkenyl group has preferably 8 or
more carbon atoms, more preferably 10 or more carbon atoms, further
preferably 12 or more carbon atoms. The number of carbon atoms is
preferably at most 19. Sufficient oil solubility cannot be obtained
with less than 8 carbon atoms which is not preferable. The alkyl or
alkenyl group may be linear or branched, and is preferably linear.
The alkyl or alkenyl group may be primary alkyl or alkenyl group,
secondary alkyl or alkenyl group, or tertiary alkyl or alkenyl
group. When the alkyl or alkenyl group is secondary alkyl or
alkenyl group, or tertiary alkyl or alkenyl group, branching occurs
preferably only at carbon atoms attached to an aromatic group.
[0049] The content of the metal-based detergent is 0.01 mass % or
more, preferably 0.03 mass % or more, more preferably 0.05 mass %
or more, and is 1 mass % or less, preferably 0.5 mass % or less,
more preferably 0.4 mass % or less, further preferably 0.3 mass %
or less, particularly preferably 0.25 mass % or less, most
preferably 0.22 mass % or less in terms of the mass of the metallic
element relative to the total mass of the lubricant oil
composition. When the content is less than 0.01 mass %, the
friction reducing effect from the addition of the metal-based
detergent tends to become insufficient, and the lubricant oil
composition often fails to provide sufficient fuel efficiency, heat
and oxidation stability, and cleaning performance. On the other
hand, when the content exceeds 1 mass %, the friction reducing
effect from the addition of the metal-based detergent tends to
become insufficient, and the fuel efficiency of the lubricant oil
composition tends to become insufficient.
[0050] The content of the boron-containing metal-based detergent is
preferably 0.01 mass % or more, more preferably 0.03 mass % or
more, further preferably 0.04 mass % or more, particularly
preferably 0.05 mass % or more, and is preferably 0.2 mass % or
less, more preferably 0.10 mass % or less, further preferably 0.08
mass % or less, particularly preferably 0.07 mass % or less in
terms of the mass of the boron element relative to the total mass
of the lubricant oil composition. When the content is less than
0.01 mass %, the friction reducing effect from the addition of the
metal-based detergent tends to become insufficient, and the fuel
efficiency, heat and oxidation stability, and cleaning performance
of the lubricant oil composition tend to become insufficient. On
the other hand, when the content exceeds 0.2 mass %, the friction
reducing effect from the addition of the metal-based detergent
tends to become insufficient, and the fuel efficiency of the
lubricant oil composition tends to become insufficient.
[0051] The boron-containing metal-based detergent has an
(MB1)/(MB2) ratio of preferably 1 or more, more preferably 2 or
more, further preferably 2.5 or more, where (MB1) is the weight of
the metallic element contained in the detergent, and (MB2) is the
weight of the boron element contained in the detergent. An
(MB1)/(MB2) ratio of less than 1 is not preferable because it may
lead to poor fuel efficiency. The (MB1)/(MB2) ratio is preferably
20 or less, more preferably or less, further preferably 10 or less,
particularly preferably 5 or less. An (MB1)/(MB2) ratio of above 20
is not preferable because it may lead to poor fuel efficiency.
(D) Ashless Friction Modifier
[0052] In the present invention, the ashless friction modifier is
at least one compound selected from amino acids having a C.sub.6-24
alkyl, alkenyl, or acyl group, and/or derivatives of such amino
acids. Examples of such compounds include the compounds represented
by the following general formula (3).
##STR00002##
[0053] Herein, R.sup.9 is a C.sub.6-24 alkyl, alkenyl, or acyl
group, R.sup.10 is a C.sub.1-4 alkyl group or hydrogen, and
R.sup.11 is hydrogen or a C.sub.1-10 alkyl group. The alkyl group
may be linear or branched, or may contain a cyclic structure. The
carbon atoms may be substituted with heteroatoms, or may be
modified with functional groups such as a hydroxyl group, a
carboxyl group, and an amino group. R.sup.12 is a C.sub.1-4 alkyl
group or hydrogen, n is 0 or 1, X is a functional group having
active hydrogen, a hydrocarbon having such a functional group, a
metal salt or an ethanolamine salt of such a functional group, or a
methoxy group.
[0054] For considerations such as solubility in the base oil,
R.sup.9 in general formula (3) is more preferably an alkyl,
alkenyl, or acyl group of 11 or more carbon atoms. For
considerations such as storage stability, the number of carbon
atoms is more preferably 20 or less. From the standpoint of
friction reducing effect, the alkyl, alkenyl, or acyl group is
preferably linear. Specific examples of such alkyl, alkenyl, and
acyl groups include alkyl group such as hexyl group, heptyl group,
octyl group, nonyl group, decyl group, undecyl group, dodecyl
group, tridecyl group, tetradecyl group, pentadecyl group,
hexadecyl group, heptadecyl group, octadecyl group, nonadecyl
group, icosyl group, heneicosyl group, docosyl group, tricosyl
group, and tetracosyl group (these alkyl groups may be linear or
branched), alkenyl group such as hexenyl group, heptenyl group,
octenyl group, nonenyl group, decenyl group, undecenyl group,
dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl
group, hexadecenyl group, heptadecenyl group, octadecenyl group,
nonadecenyl group, icocenyl group, heneicosenyl group, docosenyl
group, tricosenyl group, and tetracosenyl group (these alkenyl
groups may be linear or branched, and the double bond may occur at
any position), and acyl group having a ketone group at the terminal
of these alkyl or alkenyl groups.
[0055] For considerations such as storage stability, R.sup.10 in
general formula (3) is more preferably an alkyl group of 4 or less
carbon atoms, further preferably 3 or less carbon atoms,
particularly preferably 2 or less carbon atoms.
[0056] The alkyl group represented by R.sup.11 may be linear or
branched, or may contain a cyclic structure. The carbon atoms may
be substituted with heteroatoms, or may be modified with functional
groups such as a hydroxyl group, a carboxyl group, and an amino
group. From the standpoint of friction reducing effect and
solubility in the base oil, the alkyl group is more preferably of 2
or less carbon atoms, further preferably of 1 or less carbon atom,
particularly preferably hydrogen.
[0057] For considerations such as storage stability, R.sup.12 is
more preferably alkyl group of 4 or less carbon atoms, further
preferably 3 or less carbon atoms, particularly preferably 2 or
less carbon atoms, most preferably hydrogen.
[0058] Preferred examples of the functional group with active
hydrogen represented by X in general formula (3) include a hydroxyl
group, and an amino group. The amino group is preferably a primary
or secondary amine, particularly preferably a primary amine.
Examples of the metal salts of the active hydrogen group include
metal salts of a hydroxyl group. Preferably, --COX in general
formula (3) is a carboxyl group.
[0059] Specific examples of the hydrocarbons having a hydroxyl
group corresponding to the functional group having active hydrogen
include: dihydric alcohols such as ethylene glycol, propylene
glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol,
1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, isopreneglycol,
3-methyl-1,5-pentanediol, sorbite, catechol, resorcin,
hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A,
hydrogenated bisphenol F, and dimerdiol; trihydric alcohols such as
glycerine, 2-(hydroxymethyl)-1,3-propanediol, 1,2,3-butanetriol,
1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol,
2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol,
2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol,
2,4-dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol,
1,2,4-pentanetriol, trimethylolethane, and trimethylolpropane;
tetrahydric alcohols such as pentaerythritol, erythritol,
1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol,
1,3,4,5-hexanetetrol, diglycerin, and sorbitan; penthydric alcohols
such as adonitol, arabitol, xylitol, and triglycerine; hexahydric
alcohols such as dipentaerythritol, sorbitol, mannitol, iditol,
inositol, dulcitol, talose, and allose; and polyglycerines or
dehydrocondensation products thereof.
[0060] Examples of the metals of the hydroxyl metal salts include
alkali metals, alkali earth metals, and zinc. Examples of the
alkali metals and the alkali earth metals include sodium,
potassium, magnesium, and calcium. Preferred for improving the
persistence of the frictional effect are alkali earth metals, and
zinc.
[0061] The metal salts are preferably carboxylates with a carboxyl
structure representing --COX in general formula (3).
[0062] For considerations such as improvement of the persistence of
the frictional effect, the ashless friction modifier of the present
invention is preferably at least one kind of compounds selected
from the compounds of general formula (3). The one kind of
compounds selected from the compounds of general formula (3) may be
used alone, or as a mixture of two or more kinds of compounds.
[0063] Preferred examples of the compounds represented by general
formula (3) include N-acyl sarcosine, particularly N-oleoyl
sarcosine in which R.sup.9 is a C.sub.18 acyl group, R.sup.10 is
methyl group, R.sup.11 is hydrogen, X is hydroxyl group, and n is
0, and N-lauroyl-N-methyl-.beta.-alanine in which R.sup.9 is
lauroyl group (C.sub.12 acyl group) , R.sup.10 is methyl group,
R.sup.11 is hydrogen, R.sup.12 is hydrogen, X is hydroxyl group,
and n is 1.
[0064] The content of the ashless friction modifier is 0.01 to 10
mass %, preferably 5 mass % or less, more preferably 2 mass % or
less relative to the total mass of the composition. A content above
10 mass % is not preferable because the extra content does not
provide a further improvement in frictional characteristics, but
results in poor storage stability. The content is preferably 0.05
mass % or more, more preferably 0.1 mass % relative to the total
mass of the composition. A content below 0.01 mass % is not
preferable because it is ineffective at improving the frictional
characteristics.
(E) Antiwear Agent
[0065] The lubricant oil composition for internal combustion
engines of the present invention preferably contains zinc dialkyl
dithiophosphate (ZnDTP) of the following general formula (4) as an
antiwear agent, in addition to the foregoing additives.
##STR00003##
[0066] R.sup.13 to R.sup.16 in the general formula (4) each
independently represent hydrogen, and at least one of R.sup.13 to
R.sup.16 is a linear or branched C.sub.1-24 alkyl group. The alkyl
group maybe primary, secondary, or tertiary.
[0067] In the present invention, the zinc dialkyl dithiophosphates
may be used either alone or in a combination of two or more kinds
thereof. For improved wear resistance, it is, however, preferable
to use a zinc dithiophosphoate having a primary alkyl group
(primary ZnDTP), or a zinc dithiophosphoate having a secondary
alkyl group (secondary ZnDTP), particularly a zinc dialkyl
dithiophosphate containing secondary ZnDTP as a main component.
[0068] The content of the zinc dialkyl dithiophosphate in the
lubricant oil composition of the present invention is preferably
0.02 to 0.2 mass %, more preferably 0.03 to 0.1 mass % in terms of
the mass of the phosphorus content relative to the total mass of
the composition. A phosphorus content of less than 0.02 mass % is
insufficient in terms of wear resistance and high-temperature
cleaning performance. Above 0.2 mass %, the exhaust gas catalyst
causes serious catalyst poisoning, which is not preferable.
[0069] The lubricant oil composition for internal combustion
engines of the present invention may appropriately contain other
additives, as required, provided that the addition of such
additional components is not detrimental to the objects of the
present invention. Examples of such additives include viscosity
index improvers, pour point depressants, antioxidants, wear
inhibitors or extreme pressure agents, friction modifiers,
dispersants, anti-rusting agents, surfactants or demulsifiers, and
defoaming agents.
[0070] The viscosity index improvers may be, for example,
non-dispersive viscosity index improvers or dispersive viscosity
index improvers. Specific examples include non-dispersive or
dispersive polymethacrylate and olefin copolymers, polyisobutene,
polystyrene, ethylene-propylene copolymer, styrene-diene copolymer,
and hydrides thereof. The weight-average molecular weights of these
agents are typically 5,000 to 1,000,000. For improved
fuel-efficient performance, it is, however, preferable to use
viscosity index improvers having a weight-average molecular weight
of 100,000 to 1,000,000, preferably 200,000 to 900,000,
particularly preferably 400,000 to 800,000. In the present
invention, it is preferable for improved fuel efficiency that the
viscosity index improver is a poly(meth)acrylate-based viscosity
index improver containing 30 to 90 mol % of the structure unit
represented by the following general formula (5) , 0.1 to 50 mol %
of the structure unit represented by the following general formula
(6) , and a hydrocarbon main chain in a proportion of 0.18 or
less.
##STR00004##
[0071] In the general formula (5) , R.sup.17 represents hydrogen or
a methyl group, R.sup.18 represents a linear or branched
hydrocarbon group of 6 or less carbon atoms. In general formula (6)
, R.sup.19 represents hydrogen or a methyl group, and R.sup.20
represents a linear or branched hydrocarbon group of 16 or more
carbon atoms.
[0072] The viscosity index improver preferably has a diesel
injector PSSI (permanent shear stability index) of 30 or less.
[0073] With a PSSI of above 30, the shear stability suffers, and
the initial fuel efficiency may decrease to maintain certain levels
of kinematic viscosity or HTHS viscosity after use.
[0074] As used herein, "diesel injector PSSI" means a permanent
shear stability index of a polymer calculated with measured data
from ASTM D6278-02 (Test Method for Shear Stability of Polymer
Containing Fluids Using a European Diesel Injector Apparatus)
according to ASTM D6022-01 (Standard Practice for Calculation of
Permanent Shear Stability Index).
[0075] Examples of the pour point depressants include
polymethacrylate-based polymers, alkylated aromatic compounds,
fumarate-vinyl acetate copolymers, and ethylene-vinyl acetate
copolymers that are compatible with the lubricant oil base oil
used.
[0076] The detergent dispersant may be, for example, succinimide,
benzylamine, alkylpolyamine, polybuteneamine, or modified products
thereof with boron compounds or sulfur compounds, or an alkenyl
succinic acid ester.
[0077] The detergent dispersant is preferably a mono or bis
succinimide, more preferably a bis succinimide, particularly
preferably a boron-free bis succinimide.
[0078] The detergent dispersant has a molecular weight of
preferably 1000 or more, more preferably 5000 or more, further
preferably 7000 or more, even more preferably 9000 or more. The
molecular weight is preferably 30000 or less, more preferably 25000
or less, further preferably 20000 or less. Cleaning performance may
become insufficient when the molecular weight is 1000 or less. On
the other hand, the fuel efficiency of the engine oil composition
may greatly decrease with a molecular weight exceeding 30000.
[0079] The content of the detergent dispersant is preferably 0.1 to
15 mass %, more preferably 0.5 to 10 mass %, further preferably 1.0
to 8 mass % relative to the total mass of the engine oil
composition. Cleaning performance may become insufficient when the
detergent dispersant content is less than 0.1 mass %. On the other
hand, the fuel efficiency of the engine oil composition may greatly
decrease with a content exceeding 15 mass %.
[0080] The N content in the detergent dispersant is preferably 0.1
or more, more preferably 0.3 or more, further preferably 0.4 or
more, even more preferably 0.5 or more. The N content is preferably
2.0 or less, more preferably 1.0 or less, further preferably 0.8 or
less. Cleaning performance may become insufficient when the N
content is 0.1 or less. On the other hand, the fuel efficiency of
the engine oil composition may greatly decrease with the N content
exceeding 2.0.
[0081] The antioxidant may be a phenol- or amine-based compound or
any other compound, provided that it is selected from those
commonly used for lubricants. Examples thereof include alkylphenols
such as 2, 6-di-tert-butyl-4-methylphenol;
[0082] bisphenols such as
methylene-4,4-bis(2,6-di-tert-butyl-4-methylphenol); naphthylamines
such as phenyl-.alpha.-naphthylamine; dialkyldiphenylamines; and
phenothiazines.
[0083] Examples of the extreme pressure additives and the antiwear
agents include phosphorus compounds such as phosphoric acid esters,
phosphorous acid esters, and salts thereof; and sulfur compounds
such as disulfides, sulfurized olefins, and sulfurized grease.
[0084] The anti-rusting agents may be, for example, alkenyl
succinic acid, alkenyl succinic acid ester, polyalcohol ester,
petroleum sulfonate, or dinonylnaphthalene sulfonate.
[0085] The corrosion inhibitors may be, for example,
benzotriazole-, thiadiazole-, or imidazole-based compounds.
[0086] The defoaming agents may be, for example, silicone compounds
such as dimethyl silicone, and fluorosilicone.
[0087] These additives may be added in any amounts. Typically, the
content of the defoaming agent is 0.0005 to 0.01 mass %, the
content of the viscosity index improver is 0.05 to 20 mass %, the
content of the corrosion inhibitor is 0.005 to 0.2 mass %, and the
content of other additive is 0.05 to 10 mass % relative to the
total mass of the composition.
[0088] The lubricant oil composition for internal combustion
engines of the present invention has a kinematic viscosity at
100.degree. C. of preferably 4.0 mm.sup.2/s or more, more
preferably 6.0 mm.sup.2/s or more, further preferably 6.1
mm.sup.2/s or more, most preferably 6.2 mm.sup.2/s or more. The
kinematic viscosity at 100.degree. C. is preferably 12. 5
mm.sup.2/s or less, more preferably 9.3 mm.sup.2/s or less, further
preferably 8.5 mm.sup.2/s or less. As used herein, "kinematic
viscosity at 100.degree. C." is a kinematic viscosity at
100.degree. C. as defined by ASTM D-445. Insufficient lubricity may
result when the kinematic viscosity at 100.degree. C. is less than
4.0 mm.sup.2/s. With a kinematic viscosity at 100.degree. C. above
12.5 mm.sup.2/s, it may not be possible to obtain the necessary
low-temperature viscosity, and sufficient fuel-efficient
performance.
[0089] The lubricant oil composition has a kinematic viscosity at
40.degree. C. of preferably 4 to 50 mm.sup.2/s, preferably 40
mm.sup.2/s or less, more preferably 35 mm.sup.2/s or less. The
kinematic viscosity at 40.degree. C. is preferably 15 mm.sup.2/s or
more, more preferably 18 mm.sup.2/s or more, further preferably 20
mm.sup.2/s or more, particularly preferably 22 mm.sup.2/s or more,
most preferably 25 mm.sup.2/s or more. As used herein, "kinematic
viscosity at 40.degree. C." is a kinematic viscosity at 40.degree.
C. as defined by ASTM D-445. Insufficient lubricity may result when
the kinematic viscosity at 40.degree. C. is less than 4 mm.sup.2/s.
With a kinematic viscosity at 40.degree. C. above 50 mm.sup.2/s, it
may not be possible to obtain the necessary low-temperature
viscosity, and sufficient fuel-efficient performance.
[0090] The lubricant oil composition has a viscosity index of
preferably 120 to 400, more preferably 190 or more, further
preferably 200 or more, particularly preferably 230 or more, most
preferably 240 or more. With a viscosity index of less than 120, it
may become difficult to improve fuel efficiency while maintaining
the 150.degree. C. HTHS viscosity. A viscosity index above 400 may
result in poor evaporativity, and may cause problems due to the
insufficiency of the solubility of the additives, or of
compatibility with the sealant.
[0091] In order to improve fuel efficiency while preventing the
low-viscosity problem and maintaining durability, it is effective
to increase the HTHS viscosity at 150.degree. C. (HTHS viscosity is
also known as "high-temperature high-shear viscosity"), and to
decrease the kinematic viscosity at 40.degree. C., kinematic
viscosity at 100.degree. C., and HTHS viscosity at 100.degree. C.
It is, however, very difficult to satisfy all these conditions with
conventional lubricant oils.
[0092] The lubricant oil composition has a HTHS viscosity at
100.degree. C. of preferably 5.5 mPas or less, more preferably 5.0
mPas or less, further preferably 4.7 mPas or less, particularly
preferably 4.5 mPas or less, most preferably 4.4 mPas or less. The
HTHS viscosity at 100.degree. C. is preferably 3.0 mPas or more,
further preferably 3.5 mPas or more, particularly preferably 4.0
mPas or more, most preferably 4.1 mPas or more. As used herein,
"HTHS viscosity at 100.degree. C. " is a high-temperature
high-shear viscosity at 100.degree. C. as defined by ASTM D4683.
Insufficient lubricity may result when the HTHS viscosity at
100.degree. C. is less than 3.0 mPas. With a HTHS viscosity at
100.degree. C. above 5.5 mPas, it may not be possible to obtain the
necessary low-temperature viscosity, and sufficient fuel-efficient
performance.
[0093] The ratio of HTHS viscosity at 150.degree. C. to HTHS
viscosity at 100.degree. C. (HTHS viscosity at 150.degree. C./HTHS
viscosity at 100.degree. C.) in the lubricant oil composition of
the present invention is preferably 0.45 or more, more preferably
0.475 or more, further preferably 0.50, even more preferably 0.515
or more, particularly preferably 0.53 or more. With a ratio of HTHS
viscosity at 150.degree. C. to HTHS viscosity at 100.degree. C. of
less than 0.45, it may not be possible to obtain the necessary
low-temperature viscosity, and sufficient fuel-efficient
performance.
EXAMPLES
[0094] The present invention is described below in greater detail
using Examples and Comparative Examples. However, the present
invention is not limited to the following examples. (Examples 1 to
3, and Comparative Examples 1 to 7)
(A) Lubricant Oil Base Oil
[0095] The hydrocracked lubricant oil base oils of the following
properties were used by being mixed in the proportions shown in
Table 1.
[0096] (A-1) Kinematic viscosity at 40.degree. C.: 19.6=.sup.2/s;
kinematic viscosity at 100.degree. C.: 4.2 mm.sup.2/s; viscosity
index: 122; sulfur content: less than 10 ppm; % C.sub.P: 80.7; %
C.sub.N: 19.3; % C.sub.A: 0
[0097] (A-2) Kinematic viscosity at 40.degree. C.: 13.5 mm.sup.2/s;
kinematic viscosity at 100.degree. C.: 3.2 mm.sup.2/s; viscosity
index: 112; sulfur content: less than 10 ppm; % C.sub.P: 72.6; %
C.sub.N: 27.4; % C.sub.A: 0
[0098] The following additives were added to the lubricant oil base
oils in the proportions shown in Table 1 to prepare lubricant oil
compositions.
(B) Molybdenum-Based Friction Modifier
[0099] Molybdenum dithiocarbamate of general formula (1) in which
R.sup.1 to R.sup.4 are C.sub.8 or C.sub.13 alkyl group, and a and b
are 2. The molybdenum element concentration: 10 mass %; sulfur
content: 11 mass %
(C) Metal-Based Detergent
[0100] (C-1) Overbased Ca salicylate
[0101] Metal ratio: 2.3; C.sub.14-18 alkyl group; Ca content: 6.2
mass %; base number: 180 mgKOH/g
(C-2) Overbased boric acid Ca salicylate
[0102] Metal ratio: 2.5; C.sub.14-18 alkyl group; Ca content: 6.8
mass %; B content: 2.7 mass %; base number: 190 mgKOH/g
(C-3) Overbased boric acid Ca salicylate
[0103] Metal ratio: 1.5; C.sub.14-28 alkyl group; Ca content: 5.0
mass %; B content: 1.8 mass %; base number: 140 mgKOH/g
(D) Ashless Friction Modifier
[0104] (D-1) Oleoyl sarcosine [0105] (D-2)
N-Lauroyl-N-methyl-P-alanine [0106] (D-3) N-Lauroyl sarcosine
[0107] (D-4) Oleoyl-N-methyl-P-alanine [0108] (D-5) Alkylamine
ethylene oxide adduct [0109] (D-6) Oleylamine [0110] (D-7)
Glycerine monooleate [0111] (D-8) Oleylamide [0112] (D-9)
Oleylurea
(E) Other Additives
(E-1) ZnDTP
[0113] Secondary alkyl group; 4 and 6 carbon atoms; Zn content: 7.8
mass %; P content: 7.2 mass %; S content: 15 mass %
(E-2) Non-dispersive PMA-based viscosity index improver (Mw
=380,000; PSSI=25) (E-3) Polybutenyl succinimide
[0114] Molecular weight: 9000; N content: 0.6 mass %
(E-4) Antioxidant, defoaming agent (dimethylsilicone), and
others
[0115] The lubricant oil compositions prepared as above were each
measured for friction torque by a motoring friction test performed
under the following conditions. The average friction torque of each
lubricant oil composition was calculated, and percentage
improvement relative to the average friction torque of Comparative
Example 1 was determined (Percentage improvement=average friction
torque of Examples 1 to 7 and Comparative Examples 2 to 7/average
friction torque of Comparative Example 1). The results (%) are
presented in Table 1, along with the physical properties of the
lubricant oil compositions.
(Test Conditions)
[0116] Test Engine: Inline 4-cylinder 1800-cc engine with roller
locker arms
[0117] Oil temperature: 100.degree. C.
[0118] Engine speed: 1000 rpm
TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 4 5 6 7 1
2 3 4 5 6 7 Base oil (mass % (A-1) 70 70 70 70 70 70 70 70 70 70 70
70 70 70 relative to the total (A-2) 30 30 30 30 30 30 30 30 30 30
30 30 30 30 mass of base oil) Kinematic viscosity 40.degree. C.
17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0
17.0 of base oil (mm.sup.2/s) 100.degree. C. 3.8 3.8 3.8 3.8 3.8
3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Viscosity index of base oil 120
120 120 120 120 120 120 120 120 120 120 120 120 120 Additives (mass
% (B) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.3 0.3 0.8
relative to (C-1) 2.5 2.5 2.5 the total mass (C-2) 2.5 2.5 2.5 2.5
2.5 2.5 2.5 2.5 2.5 of composition) (C-3) 3.8 (D-1) 1.0 0.5 1.0 1.0
(D-2) 1.0 (D-3) 1.0 (D-4) 1.0 (D-5) 1.0 (D-6) 1.0 (D-7) 1.0 (D-8)
1.0 (D-9) 1.0 (E-1) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
1.0 1.0 (E-2) 15.5 15.5 15.5 15.5 15.5 15.5 15.5 15.5 15.5 15.5
15.5 15.5 15.5 15.5 (E-3) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
3.5 3.5 3.5 3.5 (E-4) 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1
1.1 1.1 1.1 Kinematic viscosity 40.degree. C. 31.5 31.5 31.5 31.5
31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 of lubricant oil
100.degree. C. 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1
8.1 composition (mm.sup.2/s) Viscosity index of 248 248 248 248 248
248 248 248 248 248 248 248 248 248 lubricant oil composition HTHS
viscosity 100.degree. C. 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7 4.7
4.7 4.7 4.7 4.7 of lubricant oil 150.degree. C. 2.6 2.6 2.6 2.6 2.6
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 composition (mPa s) Percentage
vs. Comp. 1.11 1.10 0.93 1.81 0.2 0.6 1.88 0.00 -1.14 -3.95 -0.11
-1.60 -1.14 -0.9 improvement Example 1 of motoring friction torque
(%)
[0119] As can been seen in these results, there was no friction
reducing effect in Comparative Examples 2 to 6, in which the
molybdenum-based friction modifier was used with the ashless
friction modifier that did not contain a C.sub.6-24 hydrocarbon
group, a nitrogen atom, and a carboxyl group within the molecule.
In contrast, the lubricant oil compositions that used the ashless
friction modifier containing a C.sub.6-24 hydrocarbon group, a
nitrogen atom, and a carboxyl group within the molecule clearly
showed a friction reducing effect in synergy with the modifier. As
clearly demonstrated above, the lubricant oil composition for
internal combustion engines of the present invention has notable
effects, specifically low frictional coefficient, and excellent
fuel-efficient performance.
INDUSTRIAL APPLICABILITY
[0120] The lubricant oil composition for internal combustion
engines of the present invention can preferably be used as a
fuel-efficient engine oil for, for example, gasoline engines, and
diesel engines.
* * * * *