U.S. patent application number 14/414126 was filed with the patent office on 2015-07-30 for lubricating 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 Hiroya Miyamoto.
Application Number | 20150210954 14/414126 |
Document ID | / |
Family ID | 49915925 |
Filed Date | 2015-07-30 |
United States Patent
Application |
20150210954 |
Kind Code |
A1 |
Miyamoto; Hiroya |
July 30, 2015 |
LUBRICATING OIL COMPOSITION FOR INTERNAL COMBUSTION ENGINE
Abstract
A lubricating oil composition is provided as an engine oil for
an internal combustion engine employing heat management. The
composition includes (A) a base oil having 100.degree. C. kinematic
viscosity of 3.0 to 5.0 mm.sup.2/s, (B) a boronated succinimide in
an amount of 0.007 mass percent or more as boron and in an amount
of 5 mass percent or less as the succinimide ashless dispersant,
based on total mass of the composition, (C) a phenol-based
antioxidant in an amount of 0.5 mass percent or more, and (D) a
viscosity index improver having a ratio of weight average molecular
weight and PSSI of 1.2.times.104 or greater in an amount of 0.1 to
5 percent by mass. The composition has a 150.degree. C. HTHS
viscosity of 2.0 to 2.8 mPas, a 100.degree. C. HTHS viscosity of
4.8 mPas or lower and a viscosity index of 180 or greater.
Inventors: |
Miyamoto; Hiroya;
(Chiyoda-ku, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JX Nippon Oil & Energy Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
JX NIPPON OIL & ENERGY
CORPORATION
Tokyo
JP
|
Family ID: |
49915925 |
Appl. No.: |
14/414126 |
Filed: |
July 2, 2013 |
PCT Filed: |
July 2, 2013 |
PCT NO: |
PCT/JP2013/068093 |
371 Date: |
January 12, 2015 |
Current U.S.
Class: |
508/192 |
Current CPC
Class: |
C10N 2030/54 20200501;
C10M 2209/084 20130101; C10N 2030/02 20130101; C10M 2207/226
20130101; C10N 2060/14 20130101; C10M 2207/026 20130101; C10M
2223/045 20130101; C10M 2219/068 20130101; C10M 2215/28 20130101;
C10N 2020/04 20130101; C10M 161/00 20130101; C10N 2030/04 20130101;
C10M 169/04 20130101; C10N 2040/255 20200501; C10N 2020/02
20130101; C10M 2229/041 20130101; C10N 2040/25 20130101; C10N
2040/252 20200501; C10M 2215/28 20130101; C10N 2060/14 20130101;
C10M 2219/068 20130101; C10N 2010/12 20130101; C10M 2223/045
20130101; C10N 2010/04 20130101; C10M 2207/226 20130101; C10N
2010/04 20130101; C10M 2219/068 20130101; C10N 2010/12 20130101;
C10M 2223/045 20130101; C10N 2010/04 20130101; C10M 2207/226
20130101; C10N 2010/04 20130101; C10M 2215/28 20130101; C10N
2060/14 20130101 |
International
Class: |
C10M 161/00 20060101
C10M161/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 13, 2012 |
JP |
2012-157372 |
Claims
1. A lubricating oil composition for an internal combustion engine,
the composition comprising (A) a base oil having 100.degree. C.
kinematic viscosity of 3.0 to 5.0 mm.sup.2/s, (B) a boronated
succinimide in an amount of 0.007 percent by mass or more as boron
and in an amount of 5 percent by mass or less as the succinimide
ashless dispersant, on the basis of the total mass of the
composition, (C) a phenol-based antioxidant in an amount of 0.5
percent by mass or more, and (D) a viscosity index improver having
a ratio of weight average molecular weight and PSSI of
1.2.times.104 or greater in an amount of 0.1 to 5 percent by mass,
the composition having a 150.degree. C. HTHS viscosity of 2.0 to
2.8 mPas, a 100.degree. C. HTHS viscosity of 4.8 mPas or lower and
a viscosity index of 180 or greater.
2. The lubricating oil composition for an internal combustion
engine according to claim 1, wherein a ratio of the boronated
succinimide to a non-boronated succinimide is from 1.0 to 3.0 by
weight.
3. The lubricating oil composition for an internal combustion
engine according to claim 1, wherein a ratio of a total content of
the boronated succinimide and the non-boronated succinimide to a
content of the viscosity index improver is 6 or less.
4. The lubricating oil composition for an internal combustion
engine according to claim 2, wherein a ratio of a total content of
the boronated succinimide and the non-boronated succinimide to a
content of the viscosity index improver is 6 or less.
Description
TECHNICAL FIELD
[0001] The present invention relates to lubricating oil
compositions for internal combustion engines (hereinafter also
referred to as "engine oil"). More specifically, the present
invention relates to an engine oil with excellent fuel saving
properties, suitable for diesel engines.
BACKGROUND ART
[0002] Internal combustion engines have been required to further
improve the fuel saving properties for recent environmental
measures such as control of CO.sub.2 emissions.
[0003] An improvement in fuel economy by a lubricating oil has been
carried out by reducing the working viscosity to reduce the viscous
resistance (for example, see Patent Literature 1). However, there
exists a certain viscosity necessary for lubrication of an internal
combustion engine that limits the improvement. Internal combustion
engine oils have been used as hydraulic pressure sources for
driving valves and thus need to have a certain degree of viscosity
to maintain the hydraulic pressure. Also for this reason, the
engine oils have a limitation to the reduction of the viscosity. In
order to overcome these limitations, heat management for an
internal combustion engine is being introduced. For example, the
required viscosity of an internal combustion engine oil can be
further reduced by lowering the maximum working temperature thereof
or by improving pumps of an internal combustion engine to decrease
the hydraulic pressure required for the pumps, depending on the
purposes or use conditions of the internal combustion engine.
Whereby, further fuel saving can be achieved.
CITATION LIST
Patent Literature
[0004] Patent Literature 1: Japanese Patent Application Laid-Open
Publication No. 2010-31082
SUMMARY OF INVENTION
Technical Problem
[0005] Conventional engine oils comprise a lubricating base oil
blended with a viscosity index improver, a detergent dispersant, a
friction modifier and the like to fulfill their required
properties. However, the engine oils has caused a problem that with
the conventional blend balance, they cannot be reduced in viscosity
sufficiently as engines oils for an internal combustion engine
employing the above-described heat management. That is, if the
necessary additives are used in their conventional amount ratios,
the viscosity increase caused by the additives is significant, and
thus the base oil viscosity must be significantly reduced to reduce
the viscosity of the lubricating oil composition. Such significant
reduction of the base oil viscosity causes an increase in engine
oil consumption due to an increase in evaporation loss and also
leads to failure to secure the viscosity necessary for a high shear
speed region and thus increases the risk of defective
lubrication.
[0006] The present invention has been made in view of the
above-described current situations and has an object to provides a
lubricating oil composition for an internal combustion engine that
is excellent in functions as an engine oil for an internal
combustion engine employing heat management and in particular fuel
saving properties and detergency.
Solution to Problem
[0007] The present invention has been completed as the results of
extensive studies to achieve the above object.
[0008] That is, the present invention relates to a lubricating oil
composition for an internal combustion engine comprising (A) a base
oil having 100.degree. C. kinematic viscosity of 3.0 to 5.0
mm.sup.2/s and (B) a boronated succinimide in an amount of 0.007
percent by mass or more as boron and in an amount of 5 percent by
mass or less as the succinimide ashless dispersant, on the basis of
the total mass of the composition, (C) a phenol-based antioxidant
in an amount of 0.5 percent by mass or more and (D) a viscosity
index improver having a ratio of the weight average molecular
weight and PSSI of 1.2.times.10.sup.4 or greater in an amount of
0.1 to 5 percent by mass, the composition having a 150.degree. C.
HTHS viscosity of 2.0 to 2.8 mPas, a 100.degree. C. HTHS viscosity
of 4.8 mPas or lower and a viscosity index of 180 or greater.
[0009] The present invention also relates to the foregoing
lubricating oil composition for an internal combustion engine
wherein the ratio of the boronated succinimide to the non-boronated
succinimide is from 1.0 to 3.0 by weight.
[0010] The present invention also relates to the foregoing
lubricating oil composition for an internal combustion engine
wherein the ratio of the total content of the boronated
succinimide, Component (B) and a non-boronated succinimide to the
content of the viscosity index improver, Component (D) is 6 or
less.
Advantageous Effect of Invention
[0011] According to the present invention, a lubricating oil
composition for an internal combustion engine is provided, which is
excellent in functions as an engine oil for an internal combustion
engine employing heat management and in particular fuel saving
properties and detergency.
[0012] The lubricating oil composition of the present invention is
suitably used in gasoline engines, diesel engines and gas engines
for two- and four-wheeled vehicles, power generators and
cogenerations and further not only those using fuel with a sulfur
content of 50 ppm by mass or less but also various engines of ships
and outboard motors.
DESCRIPTION OF EMBODIMENTS
[0013] The present invention will be described in detail.
[0014] The lubricating base oil of the lubricating oil composition
of the present invention may be a mineral base oil or a synthetic
base oil.
[0015] Examples of the mineral lubricating base oils include those
having a 100.degree. C. kinematic viscosity satisfying the
above-described requirement selected from: paraffinic mineral base
oils which can be produced by subjecting a lubricating oil fraction
produced by atmospheric- and/or vacuum-distillation of crude oil,
to any one of or any suitable combination of refining processes
selected from solvent deasphalting, solvent extraction,
hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining,
sulfuric acid treatment, and clay treatment; n-paraffinic base
oils; and iso-paraffinic base oils.
[0016] Examples of preferred lubricating base oils include base
oils produced using the following base oils (1) to (8) as a
feedstock by refining the feedstock and/or a lubricating oil
fraction recovered therefrom in a given refining process and
recovering a lubricating oil fraction:
[0017] (1) a distillate oil produced by atmospheric distillation of
a paraffin-base crude oil and/or a mixed-base crude oil;
[0018] (2) a whole vacuum gas oil (WVGO) produced by vacuum
distillation of the topped crude of a paraffin-base crude oil
and/or a mixed-base crude oil;
[0019] (3) a wax produced by dewaxing of lubricating oil (slack
wax) and/or a synthetic wax produced through a gas to liquid (GTL)
process (Fischer-Tropsch wax, GTL wax);
[0020] (4) a mixed oil of one or more types selected from base oils
(1) to (3) and/or an oil produced by mild-hydrocracking the mixed
oil;
[0021] (5) a mixed oil of two or more types selected from base oils
(1) to (4) above;
[0022] (6) a deasphalted oil (DAO) produced by deasphalting base
oil (1), (2) (3), (4) or (5);
[0023] (7) an oil produced by mild-hydrocracking (MHC) base oil
(6); and
[0024] (8) a mixed oil of two or more types selected from base oils
(1) to (7) above.
[0025] The above-mentioned given refining process is preferably
hydro-refining such as hydrocracking or hydrofinishing, solvent
refining such as furfural extraction, dewaxing such as solvent
dewaxing and catalytic dewaxing, clay refining with acidic clay or
active clay or chemical (acid or alkali) refining such as sulfuric
acid treatment and sodium hydroxide treatment. In the present
invention, any one or more of these refining processes may be used
in any combination and order.
[0026] The lubricating base oil used in the present invention is
particularly preferably the following base oil (9) or (10) produced
by subjecting a base oil selected from the above-described base
oils (1) to (8) or a lubricating oil fraction recovered therefrom
to a specific treatment:
[0027] (9) a hydrocracked base oil produced by hydrocrackinga base
oil selected from base oils (1) to (8) or a lubricating oil
fraction recovered from the base oil, and subjecting the resulting
product or a lubricating oil fraction recovered therefrom by
distillation, to a dewaxing treatment such as solvent or catalytic
dewaxing, optionally followed by distillation; or
[0028] (10) a hydroisomerized base oil produced by hydroisomerizing
a base oil selected from base oils (1) to (8) or a lubricating oil
fraction recovered from the base oil, and subjecting the resulting
product or a lubricating oil fraction recovered therefrom by
distillation, to a dewaxing treatment such as solvent or catalytic
dewaxing, optionally followed by distillation.
[0029] If necessary, a solvent refining process and/or a
hydrofinishing process may be carried out at appropriate timing
upon production of lubricating base oil (9) or (10).
[0030] No particular limitation is imposed on the catalyst used in
the above-described hydrocracking and hydroisomerizing. However,
the catalyst is preferably a hydrocracking catalyst comprising any
one of complex oxides having cracking activity (for example,
silica-alumina, alumina boria, or silica zirconia) or one or more
types of such complex oxides bound with a binder, used as a support
and a metal with hydrogenation capability (for example, one or more
types of metals of Groups VIa and VIII of the periodic table)
supported on the support, or a hydroisomerizing catalyst comprising
a support containing zeolite (for example, ZSM-5, zeolite beta, or
SAPO-11) and a metal with hydrogenation capability, containing at
least one or more types of metals of Group VIII of the periodic
table and supported on the support. The hydrocracking and
hydroisomerizing catalysts may be laminated or mixed so as to be
used in combination.
[0031] No particular limitation is imposed on the conditions under
which the hydrocracking and hydroisomerizing are carried out.
Preferably, the hydrogen partial pressure is from 0.1 to 20 MPa,
the average reaction temperature is from 150 to 450.degree. C., the
LHSV is from 0.1 to 3.0 hr.sup.-1, and the hydrogen/oil ratio is
from 50 to 20000 scf/b.
[0032] The 100.degree. C. kinematic viscosity of the lubricating
base oil of the present invention is necessarily 5.0 mm.sup.2/s or
lower, preferably 4.5 mm.sup.2/s or lower, particularly preferably
4.2 mm.sup.2/s or lower. Whilst, the kinematic viscosity is
necessarily 3.0 mm.sup.2/s or higher, preferably 3.4 mm.sup.2/s or
higher, more preferably 3.7 mm.sup.2/s or higher.
[0033] The 100.degree. C. kinematic viscosity used herein refers to
the 100.degree. C. kinematic viscosity determined in accordance
with ASTM D-445.
[0034] If the 100.degree. C. kinematic viscosity of the lubricating
base oil exceeds 5 mm.sup.2/s, the resulting composition would be
degraded in low temperature viscosity characteristics and may not
obtain sufficiently improved fuel saving properties. If the
100.degree. C. kinematic viscosity is lower than 3.0 mm.sup.2/s,
the resulting lubricating oil composition would be poor in
lubricity due to its insufficient oil film formation at lubricating
sites and would be large in evaporation loss of the
composition.
[0035] The viscosity index of the lubricating base oil of the
present invention is preferably 120 or greater, more preferably 125
or greater, more preferably 130 or greater, most preferably 140 or
greater. Whilst, the viscosity index is preferably 160 or less.
[0036] A viscosity index of less than 120 would not only cause the
viscosity-temperature characteristics, thermal/oxidation stability,
anti-evaporation properties to degrade but also cause the friction
coefficient to increase and likely cause the friction coefficient
to increase and cause the antiwear properties to degrade. A
viscosity index of greater than 160 would tend to degrade the low
temperature viscosity characteristics.
[0037] The viscosity index referred herein denotes the viscosity
index measured in accordance with JIS K 2283-1993.
[0038] The sulfur content of the lubricating base oil used in the
present invention depends on the sulfur content of the raw material
thereof. For example, when a raw material containing substantially
no sulfur such as a synthetic wax component produced by
Fischer-Tropsch reaction is used, a lubricating base oil containing
substantially no sulfur can be produced.
[0039] The lubricating base oil used in the present invention
contains sulfur in an amount of preferably 10 mass ppm or less,
more preferably 5 mass ppm or less, and particularly preferably
contains no sulfur with the objective of further improving
thermal/oxidation stability and lowering the sulfur content.
[0040] The % C.sub.P of the lubricating base oil used in the
present invention is preferably 70 or greater, more preferably 80
or greater, more preferably 85 or greater, most preferably 90 or
greater and preferably 95 or less.
[0041] If the % C.sub.P of the lubricating base oil is less than
70, the resulting composition would tend to be degraded in
viscosity-temperature characteristics, thermal/oxidation stability
and friction characteristics and when blended with additives, would
tend to degrade the efficacy thereof. The % C.sub.P is preferably
95% or less because the % CN of the base oil is preferably on the
order of 5% in view of solubility of additives.
[0042] The % C.sub.A of the lubricating base oil used in the
present invention is preferably 2 or less, more preferably 1 or
less, more preferably 0.8 or less, particularly preferably 0.5 or
less, most preferably 0. If the % C.sub.A of the lubricating base
oil exceeds 2, the resulting composition would tend to be degraded
in viscosity-temperature characteristics, thermal/oxidation
stability and fuel saving properties.
[0043] The % C.sub.P and % C.sub.A referred in the present
invention denote the percentage of paraffin carbon number in the
total carbon number and the percentage of the aromatic carbon
number in the total carbon number, respectively, determined by a
method (n-d-M ring analysis) in accordance with ASTM D 3238-85.
[0044] Examples of the synthetic base oil include
poly-.alpha.-olefins and hydrogenated compounds thereof; isobutene
oligomers and hydrogenated compounds thereof; isoparaffins;
alkylbenzenes; and alkylnaphthalenes, among which
poly-.alpha.-olefins are preferable.
[0045] Typical examples of poly-.alpha.-olefins include oligomers
or cooligomers of .alpha.-olefins having 2 to 32, preferably 6 to
16 carbon atoms, such as 1-octene oligomer, decene oligomer,
oligomers or cooligomers of 1-dodecene, and hydrogenated compounds
thereof.
[0046] These synthetic base oils may be those that are commercially
available if their viscosity is within the same range as the
aforesaid mineral base oils. These synthetic base oils may be each
used alone or in combination with the above-described mineral base
oils. No particular limitation is imposed on the mix ratio of these
bases oils.
[0047] The engine oil of the present invention contains a boronated
succinimide as Component (B).
[0048] In the present invention, the boronated succinimide is
preferably mixed with a non-boronated succinimide. The
non-boronated succinimide denotes succinimide before being
boronated.
[0049] Examples of the succinimide include succinimides having at
least one alkyl or alkenyl group having 40 to 400, preferably 60 to
350 carbon atoms per molecule or derivatives thereof. If the carbon
number of the alkyl or alkenyl group is fewer than 40, Component
(B) would tend to be degraded in solubility in the lubricating base
oil. Whereas, if the carbon number of the alkyl or alkenyl group is
more than 400, the resulting lubricating oil composition would be
degraded in low-temperature fluidity. The alkyl or alkenyl group
may be straight-chain or branched but is preferably a branched
alkyl or alkenyl group derived from oligomers of olefins such as
propylene, 1-butene or isobutylene or a cooligomer of ethylene and
propylene. The succinimide is preferably a mono- or
bis-succinimide.
[0050] No particular limitation is imposed on the method for
producing the succinimide. For example, a method may be used,
wherein an alkyl or alkenyl succinimide produced by reacting a
compound having an alkyl or alkenyl group having 40 to 400 carbon
atoms with maleic anhydride at a temperature of 100 to 200.degree.
C. is reacted with a polyamine. Examples of the polyamine include
diethylene triamine, triethylene tetramine, tetraethylene
pentamine, and pentaethylene hexamine.
[0051] Boronation is generally carried out by allowing succinimide
to react with boric acid to neutralize the whole or part of the
remaining amino and/or imino groups.
[0052] Examples of a method of producing a boronated succinimide
are those disclosed in Japanese Patent Publication Nos. 42-8013 and
42-8014 and Japanese Laid-Open Patent Publication Nos. 51-52381 and
51-130408. More specifically, a boronated succinimide may be
produced by mixing polyamine and polybutenylsuccinic acid
(anhydride) with a boron compound such as boric acid, a boric acid
ester, or a borate in a solvent including alcohols, organic solvent
such as hexane or xylene, or a light fraction lubricating base oil
and by heating the mixture under appropriate conditions. The boron
content of the boron acid-modified succinimide produced in this
manner is generally from 0.1 to 45 percent by mass.
[0053] No particular limitation is imposed on the boron content of
the boronated succinimide used in the present invention, which is,
however, usually from 0.1 to 3 percent by mass, preferably 0.2
percent by mass or more, more preferably 0.3 percent by mass or
more, more preferably 0.5 percent by mass or more. The boron
content is preferably 2 percent by mass or less, more preferably
1.5 percent by mass or less, more preferably 1 percent by mass or
less.
[0054] The boronated succinimide is preferably a boronated
succinimide, particularly desirously a boron-containing bis-type
succinimide, with a boron content within the above-described range.
If the boron content is more than 3 percent by mass, not only
concerns about stability are arisen, but also concerns about
influences on an exhaust-gas after-treatment system would be arisen
accompanied with an increase in sulfated ash content due to the too
much boron in the composition. If the boron content is less than
0.1 percent by mass, effects of addition of the boronated
succinimide cannot be expected.
[0055] In the present invention, the boronated succinimide is
preferably used in the form of a mixture with a non-boronated
succinimide. The ratio of the above-described boronated succinimide
and the non-boronated succinimide (boronated
succinimide/non-boronated succinimide) is preferably within the
range of 1.0 to 3.0, more preferably 1.2 or greater and preferably
2.6 or less, more preferably 2.0 or less, more preferably 1.5 or
less by weight ratio.
[0056] If the ratio of the boronated succinimide and the
non-boronated succinimide exceeds 3.0, not only concerns about
stability are arisen, but also concerns about influences on an
exhaust-gas after-treatment system would be arisen accompanied with
an increase in sulfated ash content due to the too much boron in
the composition. Whilst, the ratio is less than 1.0, effects of
addition of the boronated succinimide cannot be expected.
[0057] The reason why the mixture is preferably used in combination
is that the boronated succinimide alone results in an unstable
boronated compound, which would often precipitate and the mixture
is excellent in the balance of detergency.
[0058] The content of Component (B) of the lubricating oil
composition for an internal combustion engine according to the
present invention is necessarily 0.007 percent by mass or more,
preferably 0.01 percent by mass or more and preferably 0.1 percent
by mass or less, more preferably 0.05 percent by mass or less, more
preferably 0.02 percent by mass or less as boron on the basis of
the total mass of the lubricating oil composition for an internal
combustion engine.
[0059] This is because if the content is less than 0.007 percent by
mass or less, effects by boron cannot be expected and if the
content exceeds 0.1 percent by mass, the composition would lack in
stability.
[0060] In the present invention, the total content of the boronated
succinimide and the non-boronated succinimide is 5 percent by mass
or less on the basis of the total mass of the composition.
[0061] The molecular weight of Component (B) is determined by the
carbon number of alkyl or alkenyl group and structure of the
polyamine but is preferably 2500 or greater, more preferably 3000
or greater, more preferably 3500 or greater. Whilst, the molecular
weight is preferably 10000 or less, more preferably 7000 or less,
more preferably 5000 or less. If the molecular weight is less than
2500, the resulting composition would be less in detergency effect.
Whilst, if the molecular weight exceeds 10000, the resulting
composition would be deteriorated in low temperature viscosity.
[0062] The boronated succinimide and non-boronated succinimide are
generally provided in a state where they are dissolved in a solvent
equivalent to a lubricating base oil for manufacturing reasons. The
content referred in the present invention denotes the net content
of the compound excluding the solvent.
[0063] Therefore, for example, when succinimide dissolved in a
solvent is used, the effective concentration of the succinimide is
calculated and then succinimide is added in such an amount to be
the net amount.
[0064] For example, the effective concentration may be calculated
in the following manner. Into a 50 ml volume sack-like rubber made
from natural rubber is accurately weighed out 1 to 2 grams of an
additive solution containing the succinimide. An upper portion of
the rubber is tied with thread or the like so that the content does
not spills out from the rubber sack. The rubber sack is then placed
in a Soxhlet extractor into which a piece of filter paper has been
put to extract the solvent using heptane as an extract solvent at
50.degree. C. for 24 hours. After completion of the extraction, the
rubber sack containing the sample is allowed to stand at room
temperature for 24 hours and measured. The sample remaining in the
rubber sack is the succinimide and the effective concentration can
be calculated from the weight of the sample when placed initially
in the rubber sack.
[0065] The engine oil of the present invention contains a
phenol-based antioxidant as Component (C).
[0066] Examples of the phenol-based ashless antioxidant include:
phenol-based antioxidants containing no sulfur as a constitution
element such as 4,4'-methylenebis(2,6-di-tert-butylphenol),
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-.alpha.-dimethylamino-p-cresol,
2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol),
octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
tridecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
pentaerythrityl-tetraquis[3-(3,5-di-test-butyl-4-hydroxyphenyl)propionate-
], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and
octyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate;
phenol-based ashless antioxidants containing sulfur as a
constitutional elements such as
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-di-tert-butyl-4-hydroxybenzyl)sulfide, and
2,2'-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];
and mixtures thereof.
[0067] Among these, preferred examples include
hydroxyphenyl-substituted ester-based antioxidants that are esters
of hydroxyphenyl group-substituted fatty acids and alcohols having
4 to 12 carbon atoms such as
octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and
octyl-3-(3-metyl-5-tert-butyl-4-hydroxyphenyl) propionate) and
bisphenol-based ashless antioxidants. More preferred examples
include hydroxyphenyl-substituted ester-based antioxidants.
Phenolic compounds with a molecular weight of 240 or greater are
preferable because they are high in decomposition temperature and
thus can exhibit their effects under higher temperature
conditions.
[0068] The engine oil may further contain an amine-based ashless
antioxidant. Examples of the amine-based ashless antioxidant
include phenyl-.alpha.-naphthylamine,
alkylphenyl-.alpha.-naphthylamines and dialkyldiphenylamines.
[0069] The engine oil of the present invention contains a viscosity
index improver having a weight-average molecular weight and PSSI
ratio of 1.2.times.10.sup.4 or greater as Component (D).
[0070] The weight-average molecular weight (MW) of the viscosity
index improver used in the present invention is preferably 600,000
or less, more preferably 500,000 or less, more preferably 460,000
or less. The Mw is preferably 10,000 or greater, more preferably
50,000 or greater, more preferably 100,000 or greater, particularly
preferably 200,000 or greater.
[0071] If the viscosity index improver has a weight average
molecular weight of leas than 10,000, it would be less effective in
viscosity index enhancement when it is dissolved in a lubricating
base oil and the resulting composition would not only be poor in
fuel saving properties and low temperature viscosity
characteristics but also be high in production cost. If the
viscosity index improver has a weight-average molecular weight of
greater than 600,000, it would exert the viscosity increasing
effect too much and thus the resulting composition would not only
be poor in fuel saving properties and low temperature viscosity
characteristics but also be degraded in shear stability, solubility
in a lubricating base oil and storage stability.
[0072] The viscosity index improver used in the present invention
has a PSSI (permanent shear stability index) of necessarily 20 or
less, more preferably 17 or less, more preferably 16 or less,
particularly preferably 15 or less. If the PSSI exceeds 20, the
resulting composition would be degraded in shear stability and thus
needed to be enhanced in initial kinematic viscosity, possibly
resulting in degraded fuel saving properties. If the PSSI is less
than 1, the viscosity index improver would be less effective in
viscosity index enhancement when it is dissolved in a lubricating
base oil and thus the resulting composition would not only be poor
fuel saving properties and low temperature viscosity
characteristics but also increased in production cost. The PSSI is,
therefore, preferably 1 or greater.
[0073] The ratio of the weight-average molecular weight and PSSI
(MW/PSSI) of the viscosity index improver used in the present
invention is necessarily 1.2.times.10.sup.4 or greater, preferably
1.5.times.10.sup.4 or greater, more preferably 2.0.times.10.sup.4
or greater. If the MW/PSSI is less than 1.2.times.10.sup.4, the
resulting composition would be degraded in fuel saving properties
and low temperature startability, i.e., viscosity temperature
characteristics and low temperature viscosity characteristics.
[0074] Specific examples of the compound include non-dispersant
type or dispersant type ester group-containing viscosity index
improvers, non-dispersant type or dispersant type
poly(meth)acrylate viscosity index improvers, styrene-diene
hydrogenated copolymers, non-dispersant type or dispersant type
ethylene-.alpha.-olefin copolymers or hydrogenated compounds
thereof, polyisobutylene and hydrogenated compounds thereof,
styrene-maleic anhydride ester copolymer, polyalkylstyrenes,
(meth)acrylate-olefin copolymers and mixtures thereof.
[0075] The content of Component (D) in the lubricating oil
composition of the present invention is preferably from 0.1 to 5
percent by mass, more preferably 0.5 percent by mass or more, more
preferably from 1.0 percent by mass or more on the basis of the
total mass of the composition. The content of Component (D) is
preferably 3 percent by mass or less, more preferably 2 percent by
mass or less. If the content is less than 0.1 percent by mass, the
resulting composition would be insufficient in low temperature
characteristics. If the content exceeds 5 percent by mass, the
resulting composition would be degraded in shear stability.
[0076] As with the above-described succinimide, a viscosity index
improver is generally provided in a state where it is dissolved in
a solvent equivalent to a lubricating base oil, the content of the
viscosity index improver referred herein denote the net content
excluding the solvent.
[0077] In the present invention, the ratio of the total content of
the boronated succinimide, Component (B) and the non-boronated
succinimide to the content of the viscosity index improver,
Component (D) is 6 or less.
[0078] That is, this indicates that there is a certain limit to the
ratio of the total content of the boronated succinimide, Component
(B) and the non-boronated succinimide to the content of the
viscosity index improver, Component (D). This is because although
both Component (D) and Component (B) involve an effect on the
increase of the composition viscosity, Component (B) in particular
involve an effect largely on the increase of the low temperature
viscosity and thus it is necessary to restrain Component (B) from
contributing to the viscosity increase rate of the composition.
[0079] Therefore, the ratio of the total content of the boronated
succinimide, Component (B) and the non-boronated succinimide to the
content of the viscosity index improver, Component (D) is 6 or
less, preferably 5 or less, more preferably 4 or less, more
preferably 3.5 or less, most preferably 3 or less.
[0080] The lubricating oil composition for an internal combustion
engines of the present invention may be blended with any additives
that have been generally used in a lubricating oil depending on the
purposes in order to further enhance the properties. Examples of
such additives include metallic detergents, friction modifiers,
ashless dispersants other than Component (B), antiwear agents (or
extreme pressure additives), antioxidants other than Component (C),
corrosion inhibitors, rust inhibitors, demulsifiers, metal
deactivators, and anti-foaming agents.
[0081] Examples of the metallic detergent include normal salts
and/or basic salts of alkali metal/alkaline earth metal sulfonates,
alkali metal/alkaline earth metal phenates, and alkali
metal/alkaline earth metal salicylates. Examples of the alkali
metal include sodium and potassium. Examples of the alkaline earth
metal include magnesium, calcium and barium. Preferred are
magnesium and calcium, and particularly preferred is calcium.
[0082] Examples of the friction modifier include any compounds that
are usually used as a friction modifier for lubricating oils, for
example organic molybdenum compounds and ashless friction
modifiers.
[0083] Examples of the organic molybdenum compound include
molybdenum dithiocarbamate, molybdenum dihiophosphate,
molybdenum-amine complex, molybdenum-succinimide complex,
molybdenum salts of organic acids, and molybdenum salts of
alcohols.
[0084] Examples of the ashless friction modifier include ashless
friction modifiers such as amine compounds, fatty acid esters,
fatty acid amides, fatty acids, aliphatic alcohols, and aliphatic
ethers, each having at least one alkyl or alkenyl group having 6 to
30 carbon atoms, in particular straight-chain alkyl or alkenyl
group having 6 to 30 carbon atoms per molecule. Alternative
examples include various ashless friction modifiers as exemplified
in International Publication No. 2005/037967 Pamphlet.
[0085] In the present invention, most preferred is molybdenum
dithiocarbamate because it can mostly reduce friction.
[0086] The antiwear agent (or extreme pressure additive) may be any
antiwear agents or extreme pressure additives that are used for
lubricating oil. For example, sulfuric-, phosphoric- and
sulfuric-phosphoric extreme pressure additives may be used.
Specific examples include zinc dialkyldithiophosphate (ZnDTP),
phosphorus acid esters, thiophosphorus acid esters,
dithiophosphorus acid esters, trithiophosphorus acid esters,
phosphoric acid esters, thiophosphoric acid esters,
dithiophosphoric acid esters, trithiophosphoric acid esters, amine
salts, metal salts or derivatives thereof, dithiocarbamates, zinc
dithiocaramates, disulfides, polysulfides, sulfurized olefins and
sulfurized fats and oils. Among these antiwear agents, preferred
are sulfuric extreme pressure additives, and particularly preferred
are zinc dialkyldithiophosphate.
[0087] Examples of the corrosion inhibitor include benzotriazole-,
tolyltriazole-, thiadiazole-, and imidazole-types compounds.
[0088] Examples of the rust inhibitor include petroleum sulfonates,
alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenyl
succinic acid esters, and polyhydric alcohol esters.
[0089] Examples of the demulsifier include polyalkylene
glycol-based non-ionic surfactants such as polyoxyethylenealkyl
ethers, polyoxyethylenealkylphenyl ethers, and
polyoxyethylenealkylnaphthyl ethers.
[0090] Examples of the metal deactivator include imidazolines,
pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles,
benzotriazoles and derivatives thereof,
1,3,4-thiadiazolepolysulfide,
1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamate,
2-(alkyldithio)benzoimidazole, and
.beta.-(o-carboxybenzylthio)propionitrile.
[0091] Examples of the anti-foaming agent include silicone oil with
a 25.degree. C. kinematic viscosity of 1000 to 100,000 mm.sup.2/s,
alkenylsuccinic acid derivatives, esters of polyhydroxy aliphatic
alcohols and long-chain fatty acids, aromatic amine salts of
methylsalicylate and o-hydroxybenzyl alcohol.
[0092] When these additives are contained in the lubricating oil
composition for an internal combustion engine of the present
invention, they are contained in an amount of 0.01 to 10 percent by
mass on the total composition mass basis.
[0093] The 150.degree. C. HTHS viscosity of the lubricating oil
composition for an internal combustion engine of the present
invention is 2.8 mPas or lower, preferably 2.6 mPas or lower, more
preferably 2.4 mPas or lower and 2.0 mPas or higher, preferably 2.1
mPas or higher, more preferably 2.2 mPas or higher.
[0094] If the 150.degree. C. HTHS viscosity exceeds 2.8 mPas, the
composition may not obtain sufficient fuel saving properties. If it
is lower than 2.0 mPas, the composition would lack lubricity.
[0095] The 150.degree. C. HTHS viscosity referred herein denotes
the high temperature high shear viscosity at 100.degree. C. defined
in accordance with ASTM D4683.
[0096] The 100.degree. C. HTHS viscosity of lubricating oil
composition for an internal combustion engine of the present
invention is 4.8 mPas or lower, preferably 4.7 mPas or lower, more
preferably 4.6 mPas or lower, particularly preferably 4.5 mPas or
lower.
[0097] If the 100.degree. C. HTHS viscosity exceeds 4.8 mPas, the
resulting composition would not obtain sufficient fuel saving
properties. If the 100.degree. C. HTHS viscosity is lower than 3.9
mPas, it could cause the engine hydraulic pressure to be
insufficient and thus is preferably 3.9 mPas or higher.
[0098] The 100.degree. C. HTHS viscosity referred herein denotes
the high temperature high shear viscosity at 100.degree. C. defined
in accordance with ASTM D6616.
[0099] The HTHS viscosity (150.degree. C.)/HTHS viscosity
(100.degree. C.) is preferably 0.45 or higher, more preferably
0.047 or higher, more preferably 0.049 or higher, most preferably
0.51 or higher. This is because if the HTHS viscosity (100.degree.
C.) is lower than the HTHS viscosity (150.degree. C.), the
composition would be excellent in fuel saving properties.
[0100] The 100.degree. C. kinematic viscosity of the lubricating
oil composition for an internal combustion engine of the present
invention is preferably 8 mm.sup.2/s or lower, more preferably 7.5
mm.sup.2/s or lower, more preferably 7 mm.sup.2/s or lower, most
preferably 6.8 mm.sup.2/s or lower. The 100.degree. C. kinematic
viscosity of the lubricating oil composition for an internal
combustion engine of the present invention is preferably 4
mm.sup.2/s or higher, more preferably 5 mm.sup.2/s or higher, more
preferably 6 mm.sup.2/s or higher, most preferably 6.3 mm.sup.2/s
or higher. The 100.degree. C. kinematic viscosity used herein
refers to the 100.degree. C. kinematic viscosity determined in
accordance with ASTM D-445. If the 100.degree. C. kinematic
viscosity is lower than 4 mm.sup.2/s, the resulting lubricating oil
composition would lack lubricity. If the 100.degree. C. kinematic
viscosity exceeds 8 mm.sup.2/s, the resulting composition would not
obtain the required low temperature viscosity and sufficient fuel
saving properties.
[0101] The viscosity index of the lubricating oil composition for
an internal combustion engine of the present invention is 180 or
greater, more preferably 190 or greater, more preferably 200 or
greater, particularly preferably 210 or greater, most preferably
220 or greater. If the lubricating oil composition of the present
invention has a viscosity index of less than 180, it would be
difficult to improve the fuel saving properties while maintaining
the 150.degree. C. HTHS viscosity and to reduce the low temperature
viscosity at -35.degree. C. If the viscosity index of the
lubricating oil composition of the present invention is greater
than 300, the resulting composition would be degraded in
evaporability and cause malfunctions caused by the lack of
solubility of additives and the incompatibility with seal materials
and the viscosity index is, therefore, preferably 300 or less.
Examples
[0102] The present invention will be described in more detail below
with reference to the following Examples and Comparative Examples
but are not limited thereto.
Examples 1 to 5, Comparative Examples 1 to 5
[0103] Lubricating oil compositions of the present invention
(Example 1 to 5) and those for comparison (Comparative Examples 1
to 5) were each prepared to carry out a hot tube test. The results
are set forth in Table 1 below.
[0104] The test was carried out in accordance with JPI 5S-55-99
under conditions where the amount of samples was 10 g, the test
temperature was 300.degree. C., and the test time was 16 hours.
TABLE-US-00001 TABLE 1 Compar- Compar- Compar- Compar- Compar-
ative ative ative ative ative Base oil total Exam- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- Exam- Base Oil mass basis ple 1
ple 2 ple 3 ple 4 ple 5 ple 1 ple 2 ple 3 ple 4 ple 5 O-1 base oil
1 mass % 100 90 90 100 90 90 90 90 O-2 base oil 2 mass % 10 10 10
10 10 10 O-3 base oil 3 mass % 65 O-4 base oil 4 mass % 35 O-5 base
oil 5 mass % 100 base oil mm.sup.2/s 15.6 16.8 15.6 17.1 16.8 15.6
16.8 16.8 16.8 16.8 viscosity (40.degree. C.) base oil 3.8 4.0 3.7
3.9 4.0 3.8 4.0 4.0 4.0 4.0 viscosity (100.degree. C.) base oil 142
141 126 126 141 142 141 141 141 141 viscosity index Additives A-1
Composition mass % 1.8 1.8 1.8 1.8 0.9 3.6 3.6 3.6 1.8 1.8 total
mass basis A-2 mass % 2.3 2.3 2.3 2.3 2.3 2.3 2.3 0.0 1.1 2.3 boron
content mass % 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.000
0.005 0.011 A-3 mass % 0.8 0.8 0.8 0.8 0.8 0.3 0.3 0.8 0.8 0.3 A-4
mass % 1.4 1.3 1.3 1.5 1.5 0.8 0.7 0.7 1.4 1.3 B-1 mass % 0.4 0.4
0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 C-1 other additives mass % 5 5 5 5
5 5 5 5 5 5 boronated (A-2) + mass % 4.1 4.1 4.1 4.1 3.2 5.9 5.9
3.6 2.9 4.1 non-boronated (A-1) boronated (A-2)/ 1.3 1.3 1.3 1.3
2.5 0.6 0.6 0.0 0.6 1.3 non-boronated (A-1) succinimide amount 3.0
3.3 3.3 2.7 2.2 7.8 8.7 5.3 2.1 3.3 (A-1 + A-2)/VM amount (A-4)
Evaluation results kinematic viscosity 40.degree. C. mm.sup.2/s
26.0 27.4 28.0 28.8 25.1 28.0 29.1 27.6 25.5 25.9 100.degree. C.
mm.sup.2/s 6.6 6.6 6.7 6.7 6.5 6.5 6.5 6.5 6.5 6.6 viscosity index
231 211 209 202 229 196 190 205 225 210 HTHS viscosity 100.degree.
C. mPa s 4.5 4.6 4.6 4.6 4.5 5.0 5.2 4.7 4.5 4.6 HTHS viscosity
150.degree. C. mPa s 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 HTHS
viscosity (150.degree. C.)/ 0.51 0.50 0.50 0.50 0.51 0.46 0.44 0.49
0.51 0.50 HTHSviscosity (100.degree. C.) HTT (test temperature)
grade 5 5 5 5 4 5 5 3 2 3 300.degree. C. O-1 40.degree. C.: 15.6
mm.sup.2/s, 100.degree. C.: 3.8 mm.sup.2/s, VI: 142, sulfur
content: <10 ppm, % CP: 92.5, % CN: 7.5, % CA: 0 O-2 40.degree.
C.: 36.1 mm.sup.2/s, 100.degree. C.: 6.4 mm.sup.2/s, VI: 131,
sulfur content: <10 ppm, % CP: 80.6, % CN: 19.4, % CA: 0 O-3
40.degree. C.: 19.6 mm.sup.2/s, 100.degree. C.: 4.2 mm.sup.2/s, VI:
122, sulfur content: <10 ppm, % CP: 80.7, % CN: 19.3, % CA: 0
O-4 40.degree. C.: 13.5 mm.sup.2/s, 100.degree. C.: 3.2 mm.sup.2/s,
VI: 112, sulfur content: <10 ppm, % CP: 72.6, % CN: 27.4, % CA:
0 O-5 40.degree. C.: 17.3 mm.sup.2/s, 100.degree. C.: 3.9
mm.sup.2/s, VI: 126, sulfur content: <10 ppm, % CP: 91.4, % CN:
8.6, % CA: 0 A-1 polybutenyl succinimide, average molecular weight:
9000 A-2 boron-modified polybutenyl succinimide, average molecular
weight: 4000 B: 0.5 mass % A-3 phenol-based antioxidant (hindered
phenol) A-4 non-dispersant type polymethacrylate, weight average
molecular weight 450,000, PSSI: 5 B-1 MoDTC C-1 ZnDTP: 1 mass %,
amine-based anti-oxidant 1.3 mass %, Ca salicylate: 2.5 mass %,
dimethylsilicone: 0.002 mass %
[0105] As set forth in Table 1, the lubricating oil compositions of
Examples 1 to 5 containing all Components (A) to (D) are higher in
100.degree. C. HTHS viscosity and thus better in fuel saving
properties than the lubricating oil compositions of Comparative
Examples 1 and 2 not containing Component (B). The compositions of
the present invention are higher in grade of HTT test and thus
excellent in detergency comparing with those of Comparative Example
3 to 5 not containing Components (B) or (C).
* * * * *