U.S. patent application number 13/513234 was filed with the patent office on 2012-09-20 for lubricating oil composition.
This patent application is currently assigned to IDEMITSU KOSAN CO., LTD.. Invention is credited to Hideki Kamano.
Application Number | 20120238481 13/513234 |
Document ID | / |
Family ID | 44114983 |
Filed Date | 2012-09-20 |
United States Patent
Application |
20120238481 |
Kind Code |
A1 |
Kamano; Hideki |
September 20, 2012 |
LUBRICATING OIL COMPOSITION
Abstract
A lubricating oil composition which is excellent in wear
resistance, despite its low phosphorus content, low sulfur content
and low sulfuric acid ash content, and which exhibits excellent
friction reducing effect even when used for a DLC-treated sliding
part, is provided by compounding a specific sulfur-containing
compound and a specific polar group-containing compound in a base
oil.
Inventors: |
Kamano; Hideki;
(Ichihara-shi, JP) |
Assignee: |
IDEMITSU KOSAN CO., LTD.
Tokyo
JP
|
Family ID: |
44114983 |
Appl. No.: |
13/513234 |
Filed: |
December 1, 2010 |
PCT Filed: |
December 1, 2010 |
PCT NO: |
PCT/JP2010/071520 |
371 Date: |
June 1, 2012 |
Current U.S.
Class: |
508/509 |
Current CPC
Class: |
C10M 2215/04 20130101;
C10M 2219/09 20130101; C10M 2203/1025 20130101; C10M 2219/024
20130101; C10M 2219/022 20130101; C10M 2219/085 20130101; C10N
2040/08 20130101; C10M 2215/28 20130101; C10M 2215/064 20130101;
C10N 2030/45 20200501; C10M 2207/026 20130101; C10M 141/08
20130101; C10N 2040/255 20200501; C10M 2215/082 20130101; C10M
2219/066 20130101; C10N 2040/25 20130101; C10M 2219/082 20130101;
C10N 2080/00 20130101; C10M 2215/08 20130101; C10N 2030/06
20130101; C10N 2030/43 20200501; C10M 2207/289 20130101; C10M
135/20 20130101; C10M 2203/1006 20130101; C10M 2219/084 20130101;
C10N 2040/04 20130101; C10N 2040/252 20200501; C10N 2040/042
20200501; C10M 2215/02 20130101; C10M 2207/126 20130101; C10M
2215/042 20130101; C10M 2207/046 20130101; C10M 2223/045 20130101;
C10M 2219/106 20130101; C10N 2030/44 20200501; C10M 2209/084
20130101; C10M 2209/105 20130101; C10N 2030/42 20200501; C10M
2223/045 20130101; C10N 2010/04 20130101; C10M 2207/126 20130101;
C10M 2215/08 20130101; C10N 2060/14 20130101; C10M 2207/126
20130101; C10M 2215/042 20130101; C10N 2060/14 20130101; C10M
2207/289 20130101; C10N 2060/14 20130101; C10M 2207/026 20130101;
C10M 2207/289 20130101; C10M 2203/1025 20130101; C10N 2020/02
20130101; C10M 2223/045 20130101; C10N 2020/071 20200501; C10M
2223/045 20130101; C10N 2020/071 20200501; C10M 2203/1025 20130101;
C10N 2020/02 20130101; C10M 2223/045 20130101; C10N 2010/04
20130101; C10M 2207/126 20130101; C10M 2215/08 20130101; C10N
2060/14 20130101; C10M 2207/126 20130101; C10M 2215/042 20130101;
C10N 2060/14 20130101; C10M 2207/289 20130101; C10N 2060/14
20130101 |
Class at
Publication: |
508/509 |
International
Class: |
C10M 135/26 20060101
C10M135/26 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 3, 2009 |
JP |
2009-275771 |
Claims
1. A lubricating oil composition, comprising: (A) a base oil; (B)
at least one selected from the group consisting of a
sulfur-comprising compound of formula (I) and formula (II):
##STR00017## wherein: R.sup.1 to R.sup.12 are each independently is
a hydrogen atom; a hydrocarbon group selected from the group
consisting of an alkyl group, a cycloalkyl group, an alkenyl group,
a cycloalkenyl group, and an aryl group; or a hetero
atom-comprising group comprising an atom selected from an oxygen
atom, a nitrogen atom, and a sulfur atom, which is contained a
hydrocarbon group selected from the group consisting of an alkyl
group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
and an aryl group; each Y is independently a divalent group
selected from the group consisting of --O--, --S--, --SO--,
--SO.sub.2--, --(C.dbd.O)O--, --(C.dbd.O)NH--, --O(C.dbd.O)NH--,
--C(.dbd.O)--, --N(H)--, --NHCONH--, --N.dbd.N--,
--NH--C(.dbd.NH)--NH--, --S--C(.dbd.O)--, --NH--C(.dbd.S)--, and
--NH--C(.dbd.S)--NH--; x is an integer from 1 to 3; and each n is
independently an integer from 1 to 5; and (C) a polar
group-comprising compound comprising at least one polar group
selected from the group consisting of an amino group, an amide
group, and a hydroxyl group, and which comprises a C.sub.3 to
C.sub.24 alkyl group.
2. The composition of claim 1, wherein compound (C) is at least one
selected from the group consisting of a glycerol partial ester of a
fatty acid, a glycerol monoether compound, an amine compound, and
an amide compound.
3. The composition of claim 1, wherein compound (C) is a glycerol
monoester of a fatty acid represented by the general formula (III)
or (IV): ##STR00018## wherein each R.sup.13 is independently a
C.sub.3 to C.sub.24 alkyl group, or a glycerol monoether compound
of formula (V) or (VI): ##STR00019## wherein each R.sup.14 is
independently a C.sub.3 to C.sub.24 alkyl group.
4. The composition of claim 1, wherein the compound (C) is an amine
compound of formula (VII): ##STR00020## wherein R.sup.15 is a
C.sub.3 to C.sub.24 alkyl group and each R.sup.16 is independently
a hydrogen atom or a group comprising a hydroxyl group substituted
for a terminal hydrogen atom of a straight chained C.sub.2 to
C.sub.4 alkyl group, or an amide compound of formula (VIII):
##STR00021## wherein is a C.sub.3 to C.sub.24 alkyl group, and each
R.sup.18 is independently a hydrogen atom or a group comprising a
hydroxyl group substituted for a terminal hydrogen atom of a
straight chained C.sub.2 to C.sub.4 alkyl group.
5. The composition of claim 1, comprising a phosphorus content of
0.5% by mass or less and a sulfuric acid ash content of 0.6% by
mass or less, each based on a total mass of the composition.
6. The composition of claim 1, comprising a phosphorus content of
0% by mass and a sulfuric acid ash content of 0.1% by mass or less,
each based on a total mass of the composition.
7. The composition of claim 1, being adapted for a sliding part
which is treated with diamond-like carbon (DLC).
8. The composition of claim 1, wherein the base oil (A) has a
kinematic viscosity at 100.degree. C. of 2 to 30 mm.sup.2/s.
9. The composition of claim 1, wherein the base oil (A) has a
viscosity index of 70 or more.
10. The composition of claim 1, comprising 0.01% to 5.0% by mass of
the compound (B), based on a total mass of the composition.
11. The composition of claim 1, comprising 0.1% to 2.0% by mass of
the compound (B), based on a total mass of the composition.
12. The composition of claim 1, comprising 0.01% to 5.0% by mass of
the compound (C), based on a total mass of the composition.
13. The composition of claim 1, comprising 0.1% to 2.0% by mass of
the compound (C), based on a total mass of the composition.
14. The composition of claim 1, wherein the compound (B) of formula
(I) is at least one selected from the group consisting
bis(methoxycarbonylmethyl)disulfide,
bis(ethoxycarbonylmethyl)disulfide,
bis(n-propoxycarbonylmethyl)disulfide,
bis(isopropoxycarbonylmethyl)disulfide,
bis(n-butoxycarbonylmethyl)disulfide,
bis(n-octoxycarbonylmethyl)disulfide,
bis(n-dodecyloxycarbonylmethyl)disulfide,
bis(cyclopropoxycarbonylmethyl)disulfide,
1,1-bis(2-methoxycarbonylethyl)disulfide,
1,1-bis(3-methoxycarbonyl-n-propyl)disulfide,
1,1-bis(4-methoxycarbonyl-n-butyl)disulfide,
1,1-bis(2-ethoxycarbonylethyl)disulfide,
1,1-bis(2-n-propoxycarbonylethyl)disulfide,
1,1-bis(2-isopropoxycarbonylethyl)disulfide, and
1,1-bis(2-cyclopropoxycarbonylethyl)disulfide.
15. The composition of claim 1, wherein the compound (B) of formula
(II) is at least one selected from the group consisting of
tetramethyl dithiomalate, tetraethyl dithiomalate, tetra-1-propyl
dithiomalate, tetra-2-propyl dithiomalate, tetra-1-butyl
dithiomalate, tetra-2-butyl dithiomalate, tetraisobutyl
dithiomalate, tetra-1-hexyl dithiomalate, tetra-1-octyl
dithiomalate, tetra-1-(2-ethyl)hexyl dithiomalate,
tetra-1-(3,5,5-trimethyl)hexyl dithiomalate, tetra-1-decyl
dithiomalate, tetra-1-dodecyl dithiomalate, tetra-1-hexadecyl
dithiomalate, tetra-1-octadecyl dithiomalate, tetrabenzyl
dithiomalate, tetra-.alpha.-(methyl)benzyl dithiomalate,
tetra-.alpha.,.alpha.-dimethylbenzyl dithiomalate,
tetra-1-(2-methoxy)ethyl dithiomalate, tetra-1-(2-ethoxy)ethyl
dithiomalate, tetra-1-(2-butoxy)ethyl dithiomalate,
tetra-1-(2-ethoxy)ethyl dithiomalate, tetra-1-(2-butoxybutoxy)ethyl
dithiomalate and tetra-1-(2-phenoxy)ethyl dithiomalate.
Description
TECHNICAL FIELD
[0001] The present invention relates to a lubricating oil
composition and, more specifically, to a lubricating oil
composition which is excellent in wear resistance, despite its low
phosphorus content, low sulfur content and low sulfuric acid ash
content, and which exhibits excellent friction reducing effect even
when used for a diamond-like carbon (DLC)-treated sliding part.
BACKGROUND ART
[0002] Current automobile engines use an oxidation catalyst, a
three way catalyst, an NOx occlusion reduction catalyst, a diesel
particulate filter (DPF), etc. for purification of exhaust gases.
These exhaust gas purification devices are known to be adversely
affected by metal components, phosphorus components and sulfur
components contained in the engine oil. Thus, it is known to be
necessary to reduce these components in order to prevent the
deterioration of these devices.
[0003] Various technical developments of automobiles, etc. have
been made in recent years for the purpose of reducing fuel
consumption. For example, there may be mentioned a surface
treatment technique in sliding parts such as engines.
[0004] A zinc dithiophosphate (Zn-DTP) has been conventionally used
over the years as a wear resisting and antioxidation agent for a
lubricating oil for use in an internal combustion engine such as a
gasoline engine, a diesel engine or a gas engine and is now still
accepted as an important essential additive for such a lubricating
oil for internal combustion engines.
[0005] The zinc dithiophosphate, which generates sulfuric acid and
phosphoric acid upon being decomposed, however, may consume basic
compounds contained in the engine oil and accelerate the
deterioration of the lubricant oil with the result that oil change
intervals are extremely short. Additionally, the zinc
dithiophosphate tends to form a sludge when subjected to high
temperature conditions and to cause deterioration of the detergency
inside an engine. Moreover, the zinc dithiophosphate which
contains, in the molecule thereof, a large amount of phosphorus and
sulfur components in addition to a metal (zinc) component is
considered to cause an adverse influence on an exhaust gas
purifying device. In this circumstance, it is desired to develop a
lubricating oil composition which excels in a wear resistance
without use of the zinc dithiophosphate.
[0006] In the circumstance in which development of techniques for
surface treatment of sliding parts is being made as described
above, there is a demand for further improvement of lubricating oil
compositions. For example, when a conventional lubricating oil is
used for a sliding part which has been subjected to a DLC
treatment, there is often a case in which an expected friction
reducing effect is not achievable. Thus, there is a demand for a
lubricating oil composition which exhibits excellent friction
reducing effect, even when used for DLC-treated sliding parts, to
achieve further lower-fuel consumption.
[0007] With a view toward solving these problems, various
lubricating oil additives and lubricating oil compositions have
been hitherto proposed. For example, Patent Documents 1 to 3
disclose lubricating oil additives and lubricating oil compositions
which contain as a principle component a disulfide compound having
a specific structure. Patent Document 4 discloses an engine oil
which is alleged to be able to reduce sulfur and phosphorus that
serve as a poisoning substance of reduction catalysts and to excel
in friction reducing performance. Patent Document 5 discloses a low
friction sliding mechanism which has a sliding surface using
diamond and which is provided with a lubricating oil composition
containing a specific additive.
PRIOR ART DOCUMENT
Patent Document
[0008] Patent Document 1: JP-A-2004-262964 [0009] Patent Document
2: JP-A-2004-262965 [0010] Patent Document 3: JP-A-2008-056876
[0011] Patent Document 4: JP-A-2007-131792 [0012] Patent Document
5: JP-A-2008-56735
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0013] Although development of various lubricating oil additives
and lubricating oil compositions has been thus far been made as
described above, the lubricating oil compositions disclosed in the
above documents are not fully satisfactory when taking into
consideration that lubricating oils are generally required to
satisfy various performances, such as performance against catalytic
poisoning, wear resistance and friction reducing effect, at the
same time. In particular, it has been difficult to provide a
lubricating oil composition, which exhibits performances comparable
to or better than those of the conventional ones, without using
zinc dithiophosphate which is a very effective additive for
improving wear resistance and oxidation resistance.
[0014] The present invention has been made in view of the foregoing
circumstances and is aimed at the provision of a lubricating oil
composition which is excellent in wear resistance, despite its low
phosphorus content, low sulfur content and low sulfuric acid ash
content, and which exhibits excellent friction reducing effect even
when used for a DLC-treated sliding part.
Means for Solving the Problem
[0015] The present inventors have made an earnest study and found
that the above-described object can be achieved by using a specific
sulfur-containing compound in combination with a specific polar
group-containing compound. The present invention has been completed
based on such finding.
[0016] Namely, the present invention provides:
<1> A lubricating oil composition comprising
[0017] a base oil, (A) at least one selected from sulfur-containing
compounds represented by the general formulas (I) and (II) shown
below, and (B) a polar group-containing compound which has at least
one polar group selected from amino groups, amide groups and a
hydroxyl group and which has a C.sub.3 to C.sub.24 alkyl group;
##STR00001##
[0018] (in the above formulas, R.sup.1 to R.sup.12 each
independently represent a hydrogen atom; a hydrocarbon group
selected from alkyl groups, cycloalkyl groups, alkenyl groups,
cycloalkenyl groups and aryl groups; or a hetero atom-containing
group having an atom which is selected from an oxygen atom, a
nitrogen atom and a sulfur atom and which is contained in the above
hydrocarbon group; Ys each independently represent a divalent group
selected from --O--, --S--, --SO--, --SO.sub.2--, --(C.dbd.O)O--,
--(C.dbd.O)NH--, --O(C.dbd.O)NH--, --C(.dbd.O)--, --N(H)--,
--NHCONH--, --N.dbd.N--, --NH--C(.dbd.NH)--NH--, --S--C(.dbd.O)--,
--NH--C(.dbd.S)-- and --NH--C(.dbd.S)--NH--; x represents an
integer of 1 to 3; and ns each independently represent an integer
of 1 to 5);
<2> The lubricating oil composition according to above
<1>, wherein (B) the polar group-containing compound, which
has at least one polar groups selected from amino groups, amide
groups and a hydroxyl group and which has a C.sub.3 to C.sub.24
alkyl group, is at least one compound selected from the group
consisting of glycerol partial esters of fatty acids, glycerol
monoether compounds, amine compounds and amide compounds; <3>
The lubricating oil composition according to above <1>,
wherein (B) the polar group-containing compound, which has at least
one polar groups selected from amino groups, amide groups and a
hydroxyl group and which has a C.sub.3 to C.sub.24 alkyl group, is
a glycerol monoester of a fatty acid represented by the general
formula (III) or (IV) shown below or a glycerol monoether compound
represented by the general formula (V) or (VI) shown below:
##STR00002##
wherein R.sup.13 and R.sup.14 each independently represent a
C.sub.3 to C.sub.24 alkyl group; <4> The lubricating oil
composition according to about <1>, wherein (B) the polar
group-containing compound, which has at least one polar groups
selected from amino groups, amide groups and a hydroxyl group and
which has a C.sub.3 to C.sub.24 alkyl group, is an amine compound
represented by the general formula (VII) shown below or an amide
compound represented by the general formula (VIII) shown below:
##STR00003##
wherein R.sup.15 and R.sup.17 each independently represent a
C.sub.3 to C.sub.24 alkyl group, and R.sup.16 and R.sup.18 each
independently represent a hydrogen atom or a group having a
hydroxyl group substituted for a terminal hydrogen atom of a
straight chained C.sub.2 to C.sub.4 alkyl group; <5> The
lubricating oil composition according to any one of above <1>
to <4>, wherein the lubricating oil composition has a
phosphorus content of 0.5% by mass or less and a sulfuric acid ash
content of 0.6% by mass or less, each based on the total mass of
the lubricating oil composition; <6> The lubricating oil
composition according to any one of above <1> to <5>,
wherein the lubricating oil composition has a phosphorus content of
0% by mass and a sulfuric acid ash content of 0.1% by mass or less,
each based on the total mass of the lubricating oil composition;
and <7> The lubricating oil composition according to any one
of above <1> to <6>, wherein the lubricating oil
composition is used for a sliding part which has been treated with
diamond-like carbon (DLC).
Effect of the Invention
[0019] According to the present invention, there is provided a
lubricating oil composition which is excellent in wear resistance,
despite its low phosphorus content, low sulfur content and a low
sulfuric acid ash content, and which exhibits excellent friction
reducing effect even when used for a DLC-treated sliding part.
EMBODIMENTS OF THE INVENTION
[0020] The lubricating oil composition of the present invention is
characterized in that a specific sulfur-containing compound and a
specific polar group-containing compound are compounded in a base
oil.
Base Oil:
[0021] The base oil used in the present invention is not
specifically limited and may be appropriately selected from any
mineral oils and synthetic oils that are conventionally used as a
base oil for lubricant oils.
[0022] Examples of the mineral oils include those which are
obtained by subjecting a lube-oil distillate (which is obtained by
vacuum distillation of an atmospheric residue produced by
atmospheric distillation of a crude oil) to one or more refining
treatments such as solvent deasphalting, solvent extraction,
hydrocracking, solvent dewaxing, catalytic dewaxing and
hydrorefining, and those which are produced by isomerizing waxes or
GTL waxes.
[0023] Examples of the synthetic oils include polybutene,
polyolefins (.alpha.-olefin homopolymers and copolymers (such as
ethylene-.alpha.-olefin copolymers)), various esters (such as
polyol esters, dibasic acid esters and phosphoric acid esters),
various ethers (such as polyphenyl ethers), polyglycols, alkyl
benzenes and alkyl naphthalenes. Among these synthetic oils,
particularly preferred are polyolefins and polyol esters.
[0024] In the present invention, the above mineral oils may be used
alone or in combination of two or more thereof as the base oil.
Also, the above synthetic oils may be used alone or in combination
of two or more thereof. Further, one or more mineral oils may be
used in combination with one or more synthetic oils.
[0025] The viscosity of the base oil is not specifically limited.
However, it is preferred that the base oil have a kinematic
viscosity at 100.degree. C. of 2 to 30 mm.sup.2/s, more preferably
3 to 15 mm.sup.2/s, still more preferably 4 to 10 mm.sup.2/s.
[0026] When the kinematic viscosity at 100.degree. C. is 2
mm.sup.2/s or more, an evaporation loss is small. When the
kinematic viscosity is 30 mm.sup.2/s or less, a power loss by
viscosity resistance can be suppressed so that a fuel consumption
improving effect is obtainable.
[0027] It is also preferred that the base oil have a % C.sub.A
value of 3.0 or less as measured by ring analysis and a sulfur
content of 50 ppm by mass or less. As used herein, the term "%
C.sub.A value as measured by ring analysis" means a proportion
(percentage) of an aromatic component which is calculated by the
n-d-M ring analysis method. The sulfur content as used herein means
the value as measured according to JIS K 2541.
[0028] The base oil having a % C.sub.A value of 3.0 or less and a
sulfur content of 50 ppm by mass or less exhibits good oxidation
stability and can give a lubricant oil composition that can
suppress an increase of the acid value and formation of a sludge.
The % C.sub.A value is more preferably 1.0 or less, still more
preferably 0.5 or less. The sulfur content is more preferably 30
ppm by mass or less.
[0029] It is further preferred that the base oil have a viscosity
index of 70 or more, more preferably 100 or more, still more
preferably 120 or more. When the viscosity index of the base oil is
70 or more, a change in viscosity of the base oil by a change in
temperature is small.
Sulfur-Containing Compound:
[0030] The lubricating oil composition of the present invention
contains a sulfur-containing compound represented by the following
general formula (I) or (II):
##STR00004##
[0031] In the general formulas (I) and (II), R.sup.1 to R.sup.12
each independently represent a hydrogen atom; a hydrocarbon group
selected from alkyl groups, cycloalkyl groups, alkenyl groups,
cycloalkenyl groups and aryl groups; or a hetero atom-containing
group having an atom which is selected from an oxygen atom, a
nitrogen atom and a sulfur atom and which is contained in the above
hydrocarbon group.
[0032] The alkyl group represented by R.sup.1 to R.sup.12 is
preferably a C.sub.1 to C.sub.30 alkyl group, preferably a C.sub.1
to C.sub.24 alkyl group. Specific examples of the alkyl group
include n-butyl groups, isobutyl groups, sec-butyl groups,
tert-butyl groups, various hexyl groups, various octyl groups,
various decyl groups, various dodecyl groups, various tetradecyl
groups, various hexadecyl groups, various octadecyl groups and
various icosyl groups. The alkyl group may be substituted with an
aromatic group, examples of which include a benzyl group and a
phenethyl group.
[0033] The cycloalkyl group represented by R.sup.1 to R.sup.12 is
preferably a C.sub.3 to C.sub.30 cycloalkyl group, more preferably
a C.sub.3 to C.sub.24 cycloalkyl group. Specific examples of the
cycloalkyl group include a cyclopropyl group, a cyclopentyl group,
a cyclohexyl group, a methylcyclopentyl group, a
dimethylcyclopentyl group, a methylethylcyclopentyl group, a
diethylcyclopentyl group, a methylcyclohexyl group, a
dimethylcyclohexyl group, a methylethylcyclohexyl group and a
diethylcyclohexyl group. The cycloalkyl group may be substituted
with an aromatic group, examples of which include a
phenylcyclopentyl group and a phenylcyclohexyl group.
[0034] The alkenyl group represented by R.sup.1 to R.sup.12 is
preferably a C.sub.2 to C.sub.30 alkenyl group, more preferably a
C.sub.2 to C.sub.24 alkenyl group. Specific examples of the alkenyl
group include a vinyl group, an allyl group, a 1-butenyl group, a
2-butenyl group, a 3-butenyl group, 1-methylvinyl group, a
1-methylallyl group, a 1,1-dimethylallyl group, a 2-methylallyl
group, a nonenyl group, a decenyl group and an octadecenyl group.
The alkenyl group may be substituted with an aromatic group.
[0035] The cycloalkenyl group represented by R.sup.1 to R.sup.12 is
preferably a C.sub.3 to C.sub.30 cycloalkenyl group, more
preferably a C.sub.3 to C.sub.24 cycloalkenyl group. Specific
examples of the cycloalkenyl group include a cyclobutenyl group and
a methylcyclobutenyl group. The cycloalkenyl group may be
substituted with an aromatic group.
[0036] The aryl group represented by R.sup.1 to R.sup.12 is
preferably a C.sub.6 to C.sub.30 aryl group, more preferably a
C.sub.6 to C.sub.24 aryl group. Specific examples of the aryl group
include a phenyl group, a tolyl group, a xylyl group, a naphthyl
group, a butylphenyl group, an octylphenyl group and a nonylphenyl
group.
[0037] In the general formulas (I) and (II), Ys each independently
represent a divalent group selected from --O--, --S--, --SO--,
--SO.sub.2--, --(C.dbd.O)O--, --(C.dbd.O)NH--, --O(C.dbd.O)NH--,
--C(.dbd.O)--, --N(H)--, --NHCONH--, --N.dbd.N--,
--NH--C(.dbd.NH)--NH--, --S--C(.dbd.O)--, --NH--C(.dbd.S)-- and
--NH--C(.dbd.S)--NH--.
[0038] In the general formulas (I) and (II), x is an integer of 1
to 3, preferably 2, and ns each independently represent an integer
of 1 to 5, preferably 1 or 2.
[0039] As the sulfur-containing compound represented by the general
formula (I), there may be mentioned, for example, compounds of the
formulas shown below:
##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009##
##STR00010## ##STR00011##
[0040] The following compounds are also examples of the compound
represented by the general formula (I), i.e. such examples include:
bis(methoxycarbonylmethyl)disulfide,
bis(ethoxycarbonylmethyl)disulfide,
bis(n-propoxycarbonylmethyl)disulfide,
bis(isopropoxycarbonylmethyl)disulfide,
bis(n-butoxycarbonylmethyl)disulfide,
bis(n-octoxycarbonylmethyl)disulfide,
bis(n-dodecyloxycarbonylmethyl)disulfide,
bis(cyclopropoxycarbonylmethyl)disulfide,
1,1-bis(2-methoxycarbonylethyl)disulfide,
1,1-bis(3-methoxycarbonyl-n-propyl)disulfide,
1,1-bis(4-methoxycarbonyl-n-butyl)disulfide,
1,1-bis(2-ethoxycarbonylethyl)disulfide,
1,1-bis(2-n-propoxycarbonylethyl)disulfide,
1,1-bis(2-isopropoxycarbonylethyl)disulfide and
1,1-bis(2-cyclopropoxycarbonylethyl)disulfide.
[0041] Specific examples of the compound represented by the general
formula (II) include tetramethyl dithiomalate, tetraethyl
dithiomalate, tetra-1-propyl dithiomalate, tetra-2-propyl
dithiomalate, tetra-1-butyl dithiomalate, tetra-2-butyl
dithiomalate, tetraisobutyl dithiomalate, tetra-1-hexyl
dithiomalate, tetra-1-octyl dithiomalate, tetra-1-(2-ethyl)hexyl
dithiomalate, tetra-1-(3,5,5-trimethyl)hexyl dithiomalate,
tetra-1-decyl dithiomalate, tetra-1-dodecyl dithiomalate,
tetra-1-hexadecyl dithiomalate, tetra-1-octadecyl dithiomalate,
tetrabenzyl dithiomalate, tetra-.alpha.-(methyl)benzyl
dithiomalate, tetra-.alpha.,.alpha.-dimethylbenzyl dithiomalate,
tetra-1-(2-methoxy)ethyl dithiomalate, tetra-1-(2-ethoxy)ethyl
dithiomalate, tetra-1-(2-butoxy)ethyl dithiomalate,
tetra-1-(2-ethoxy)ethyl dithiomalate, tetra-1-(2-butoxybutoxy)ethyl
dithiomalate and tetra-1-(2-phenoxy)ethyl dithiomalate.
[0042] In the present invention the sulfur-containing compounds
represented by the general formulas (I) or (II) may be used singly
or as a mixture of two or more thereof. The compounding amount of
the sulfur-containing compound is preferably 0.01% to 5.0% by mass,
more preferably 0.1% to 2.0% by mass, based on the total mass of
the composition. When the compounding amount is 0.01% by mass or
more, a sufficient wear resistance is obtainable. When the
compounding amount exceeds 5.0% by mass, there is a possibility
that the effect proportional to the amount added is not
obtainable.
Polar Group-Containing Compound:
[0043] The lubricating oil composition of the present invention
contains a polar group-containing compound which has at least one
polar group selected from amino groups, amide groups and a hydroxyl
group and which has an alkyl group having a specific number of
carbon atoms
[0044] The polar group-containing compound used in the present
invention is a compound having a C.sub.3 to C.sub.24, preferably
C.sub.8 to C.sub.20 alkyl group. When the number of carbon atoms is
less than 3, the solubility of the compound is low. Although better
friction reducing effect is generally obtainable as the number of
carbon atoms increases, an effect proportional to the increased
number of carbon atoms is hardly obtainable, when the number of
carbon atoms exceeds 24.
[0045] As the polar group-containing compound, there may be
mentioned, for example, those which are selected from glycerol
partial esters of fatty acids, glycerol monoether compounds, amine
compounds and amide compounds and which have the above-described
alkyl group.
[0046] The glycerol partial ester of a fatty acid may be, for
example, a compound obtained by reaction of glycerol with a fatty
acid. Examples of the fatty acid include acetic acid, propionic
acid, butanoic acid (butyric acid), pentanoic acid (valeric acid),
isopentanoic acid (isovaleric acid), hexanoic acid (caproic acid),
heptanoic acid, isoheptanoic acid, octanoic acid (caprylic acid),
2-ethylhexanoic acid, isooctanoic acid, nonanoic acid (pelargonic
acid), isononanoic acid, decanoic acid (capric acid), isodecanoic
acid, undecanoic acid, isoundecanoic acid, dodecanoic acid (lauric
acid), isododecanoic acid, tridecanoic acid, isotridecanoic acid,
tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic
acid), octadecanoic acid (stearic acid), isostearic acid,
eicosanoic acid (arachidic acid), docosanoic acid (behenic acid),
tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotic
acid), octacosanoic acid (montanic acid), 10-undecenoic acid,
zomaric acid, oleic acid, elaidic acid, linoleic acid, linolenic
acid, gadoleic acid, erucic acid and selacholeic acid. A mixed
fatty acid obtainable from natural fats and oils may also be used.
Among these fatty acids, C.sub.10 to C.sub.18 fatty acids are
preferred, C.sub.10 to C.sub.12 saturated fatty acids are more
preferred, oleic acid and elaidic acid are further preferred and
oleic acid is most preferred from the standpoint of the friction
reducing effect of the lubricant oil.
[0047] As the glycerol partial ester of a fatty acid, there may be
mentioned, for example, glycerol monoesters of fatty acids
represented by the general formulas (III) and (IV) shown below.
These compounds may be obtained by, for example, direct
esterification between a fatty acid and glycerol or
interesterification of a fat and oil with glycerol.
##STR00012##
[0048] In the general formulas (III) and (IV), R.sup.13s each
independently represent a C.sub.3 to C.sub.24 alkyl group. In the
present invention, the glycerol monoesters of fatty acids
represented by the general formulas (III) and (IV) may be used
singly or as a mixture thereof. In use of these glycerol monoesters
of fatty acids, glycerol diesters and/or triesters of fatty acids
may be contained therein.
[0049] The glycerol monoether compounds may be, for example,
compounds obtained by reaction of glycerol with an aliphatic
alcohol. Examples of the aliphatic alcohol include propanol,
butanol, oleyl alcohol and stearyl alcohol. Above all, from the
standpoint of friction reducing effect of the lubricant oil, oleyl
alcohol and stearyl alcohol are preferred, and oleyl alcohol is
particularly preferred.
[0050] As the glycerol monoether compound, there may be mentioned,
for example, glycerol monoether compound represented by the general
formulas (V) and (VI) shown below:
##STR00013##
[0051] In the general formulas (V) and (VI), R.sup.14s each
independently represent a C.sub.3 to C.sub.24 alkyl group. In the
present invention, the glycerol monoether compounds represented by
the general formula (V) and (VI) may be used singly or as a mixture
thereof. In use of these glycerol monoether compounds, glycerol
diethers and/or glycerol triethers may be contained therein.
[0052] Examples of the amine compound include alkylamine compounds
and alkanolamine compounds. The alkyl group of the alkylamine
compound may be the alkyl group which is contained in the
above-described fatty acids. As the amine compound, there may be
mentioned, for example, those represented by the following general
formula (VII):
##STR00014##
[0053] In the general formula (VII), R.sup.15 represents a C.sub.3
to C.sub.24 alkyl group, and R.sup.16s each independently represent
a hydrogen atom or a group having a hydroxyl group substituted for
a terminal hydrogen atom of a straight chained C.sub.2 to C.sub.4
alkyl group (such as --(CH.sub.2).sub.2--OH). In the present
invention, the amine compounds represented by the general formula
(VII) may be used singly or as a mixture thereof.
[0054] Specific examples of the amine compounds include
monoethanolamine, diethanolamine, triethanolamine,
N-methylethanolamine, N,N-dimethylethanolamine,
N-ethylethanolamine, N,N-diethylethanolamine,
N-isopropylethanolamine, N,N-diisopropylethanolamine,
monoisopropanolamine, diisopropanolamine, triisopropanolamine,
N-methylisopropanolamine, N,N-dimethylisopropanolamine,
N-ethylisopropanolamine, N,N-diethylisopropanolamine,
N-isopropylisopropanolamine, N,N-diisopropylisopropanolamine,
mono-n-propanolamine, di-n-propanolamine, tri-n-propanolamine,
N-methyl-n-propanolamine, N,N-dimethyl-n-propanolamine,
N-ethyl-n-propanolamine, N,N-diethyl-n-propanolamine,
N-isopropyl-n-propanolamine, N,N-diisopropyl-n-propanolamine,
monobutanolamine, dibutanolamine, tributanolamine,
N-methylbutanolamine, N,N-dimethylbutanolamine,
N-ethylbutanolamine, N,N-diethylbutanolamine,
N-isopropylbutanolamine and N,N-diisopropylbutanolamine.
[0055] As the amide compound, there may be mentioned compounds
obtainable by reaction of mono- to tetravalent carboxylic acid with
an alkylamine or an alkanolamine.
[0056] The monovalent carboxylic acid may have an alkyl group such
a hexyl group, a heptyl group, an octyl group, a nonyl group, a
decyl group, an undecyl group, a dodecyl group, a tridecyl group, a
tetradecyl group, a pentadecyl group, a hexadecyl group, a
heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl
group, a pentaicosyl group, a docosyl group, a tricosyl group, a
tetracosyl group, a pentacosyl group, a hexacosyl group, a
heptacosyl group, an octacosyl group, a nonacosyl group and a
triacontyl group.
[0057] Examples of the monovalent carboxylic acid include caproic
acid, caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachidic acid, behenic acid and
lignoceric acid. Examples of the di- to tetravalent carboxylic
acids include polycarboxylic acids such as oxalic acid, phthalic
acid, trimellitic acid and pyromellitic acid.
[0058] As the amide compound, there may be mentioned a compound
represented by the following general formula (VIII).
##STR00015##
[0059] In the general formula (VIII), R.sup.17 represents a C.sub.3
to C.sub.24 alkyl group, and R.sup.18s each independently represent
a hydrogen atom or a group having a hydroxyl group substituted for
a terminal hydrogen atom of a straight chained C.sub.2 to C.sub.4
alkyl group (such as --(CH.sub.2).sub.2--OH). In the present
invention, the amide compounds represented by the general formula
(VIII) may be used singly or as a mixture thereof.
[0060] Specific examples of the amide compound include oleic acid
monoethanolamide, oleic acid diethanolamide, oleic acid
monopropanolamide and oleic acid dipropanolamide.
[0061] The polar group-containing compound used in the present
invention may also be a compound obtainable by reaction of the
above-described polar group-containing compound with a molybdenum
compound. Examples of the molybdenum compound include molybdenum
oxide, molybdenum halide and molybdic acid. In this reaction, the
molybdenum compound is preferably used in a molar ratio of 0.01 to
10 moles, more preferably 0.05 to 5 moles, per mole of the polar
group-containing compound.
[0062] The reaction may be carried out using a solvent, for example
an organic solvent such as a hydrocarbon oil, hexane, heptane,
octane, toluene and xylene.
[0063] The reaction temperature for the above reaction is not
specifically limited but is preferably 50 to 250.degree. C., more
preferably 100 to 200.degree. C.
[0064] The polar group-containing compound used in the present
invention may also be a compound obtainable by reaction of the
above-described polar group-containing compound with a boron
compound. Examples of the boron compound include boron oxide, a
boron halide, boric acid, boric anhydride and an ester of boric
acid. In this reaction, the boron compound is preferably used in a
molar ratio of 0.01 to 10 moles, more preferably 0.05 to 5 moles,
per mole of the polar group-containing compound.
[0065] The reaction may be carried out using a solvent, for example
an organic solvent such as a hydrocarbon oil, hexane, heptane,
octane, toluene and xylene.
[0066] The reaction temperature for the above reaction is not
specifically limited but is preferably 50 to 250.degree. C., more
preferably 100 to 200.degree. C.
[0067] In the present invention, the polar group-containing
compounds may be used singly or as a mixture thereof. The
compounding amount of the polar group-containing compound is
preferably 0.01% to 5.0% by mass, more preferably 0.1% to 2.0% by
mass, based on the total mass of the composition. When the
compounding amount is 0.01% by mass or more, a sufficient friction
reducing effect is obtainable. When the compounding amount is 5.0%
by mass or more, there is a possibility that undissolved residues
may be present.
[0068] In the lubricating oil composition of the present invention,
a customarily employed additive may be compounded as long as the
effect thereof is not adversely affected. Examples of the additive
include an antioxidant, an ashless dispersant, a metallic
detergent, a viscosity index improver, a pour point depressant, a
metal deactivator, a rust inhibitor and a defoaming agent.
[0069] The above-mentioned antioxidant is preferably a
phosphorus-free antioxidant. Examples of the phosphorus-free
antioxidant include a phenol-based antioxidant, an amine-based
antioxidant, a molybdenum/amine complex-based antioxidant and a
sulfur-based antioxidant.
[0070] Specific examples of the phenol-based antioxidant include
4,4'-methylenebis(2,6-di-t-butylphenol),
4,4'-bis(2,6-di-t-butylphenol), 4,4'-bis(2-methyl-6-t-butylphenol),
2,2'-methylenebis(4-ethyl-6-t-butylphenol),
2,2'-methylenebis(4-methyl-6-t-butylphenol),
4,4'-butylidenebis(3-methyl-6-t-butylphenol),
4,4'-isopropylidenebis(2,6-di-t-butylphenol),
2,2'-methylenebis(4-methyl-6-nonylphenol),
2,2'-isobutylidenebis(4,6-dimethylphenol),
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,
2,4-dimethyl-6-t-butylphenol, 2,6-di-t-amyl-p-cresol,
2,6-di-t-butyl-4-(N,N'-dimethylaminomethylphenol),
4,4'-thiobis(2-methyl-6-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
2,2'-thiobis(4-methyl-6-t-butylphenol),
bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide,
bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide,
n-octyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate,
n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, and
2,2'-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate].
[0071] Above all, especially preferred are bisphenol-based
antioxidants and ester group-containing phenol-based
antioxidants.
[0072] Specific examples of the amine-based antioxidant include
monoalkyldiphenylamines such as monooctyldiphenylamine and
monononyldiphenylamine; dialkyldiphenylamines such as
4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine,
4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine,
4,4'-dioctyldiphenylamine and 4,4'-dinonyldiphenylamine;
polyalkyldiphenylamines such as tetrabutyldiphenylamine,
tetrahexyldiphenylamine, tetraoctyldiphenylamine and
tetranonyldiphenylamine; .alpha.-naphthylamine;
phenyl-.alpha.-naphthylamine; and alkyl-substituted
phenyl-.alpha.-naphthylamines such as
butylphenyl-.alpha.-naphthylamine,
pentylphenyl-.alpha.-naphthylamine,
hexylphenyl-.alpha.-naphthylamine,
heptylphenyl-.alpha.-naphthylamine,
octylphenyl-.alpha.-naphthylamine and
nonylphenyl-.alpha.-naphthylamine.
[0073] Above all, the dialkyldiphenylamine-based and
naphthylamines-based antioxidants are preferred.
[0074] As the molybdenum/amine complex-based antioxidants, there
may be mentioned, for example, hexavalent molybdenum compounds.
Specific examples of such compounds include those which are
obtained by reacting molybdenum trioxide and/or molybdic acid with
an amine compound and those which are obtained by the production
method described in JP-A-2003-252887.
[0075] The amine compound to be reacted with the hexavalent
molybdenum compound is not particularly limited, and there may be
mentioned monoamines, diamines, polyamines and alkanol amines.
Specific examples of the amine compound include alkyl amines having
an C.sub.1 to C.sub.30 alkyl group or groups (the alkyl group may
be either linear or branched) such as methylamine, ethylamine,
dimethylamine, diethylamine, methylethylamine and
methylpropylamine; alkenyl amines containing a C.sub.2 to C.sub.30
alkenyl group or groups (the alkenyl group may be linear or
branched) such as ethenyl amine, propenyl amine, butenyl amine,
octenyl amine and oleyl amine; alkanol amines containing a C.sub.1
to C.sub.30 alkanol group or groups (the alkanol group may be
linear or branched) such as methanol amine, ethanol amine, methanol
ethanol amine and methanol propanol amine; alkylene diamines
containing a C.sub.1 to C.sub.30 alkylene group or groups such as
methylenediamine, ethylenediamine, propylenediamine and
butylenediamine; polyamines such as diethylenetriamine,
triethylenetetramine, tetraethylenepentamine and
pentaethylenehexamine; compounds, such as undecyldiethylamine,
undecyldiethanol amine, dodecyldipropanol amine, oleyldiethanol
amine, oleylpropylenediamine and stearyltertraethylenepentamine,
which are obtained by further introducing a C.sub.8 to C.sub.20
alkyl or alkenyl group into the above monoamines, diamines or
polyamines; heterocyclic compounds such as imidazoline;
alkyleneoxide adducts of these compounds; and mixtures of these
compounds.
[0076] In addition, as the molybdenum/amine complex-based
antioxidants, there may be mentioned, for example,
sulfur-containing molybdenum complexes of succinic imide as
described in JP-B-3-22438 and JP-A-2004-2866.
[0077] As the sulfur-based antioxidant, there may be mentioned, for
example, phenothiazine, pentaerythritol-tetrakis-(3-lauryl
thiopropionate), didodecyl sulfide, dioctadecyl sulfide, didodecyl
thiodipropionate, dioctadecyl thiodipropionate, dimyristyl
thiodipropionate, dodecyloctadecyl thiodipropionate and
2-mercaptobenzoimidazole.
[0078] Among these antioxidants, from the standpoint of reducing a
metal content and a sulfur content, phenol-based antioxidants and
amine-based antioxidants are preferred. The above antioxidants may
be used singly or as a mixture of two or more thereof. From the
standpoint of improved oxidation stability, a mixture of one or
more kinds of phenol-based antioxidants and one or more kinds of
amine-based oxidants is preferably used.
[0079] The compounding amount of the antioxidant is generally 0.1%
to 5% by mass, more preferably from 0.1% to 3% by mass, based on
the total mass of the composition.
[0080] As the above-mentioned ashless dispersant, there may be used
any ashless dispersant which is generally used for lubricant oils.
Examples of the ashless dispersant include a mono-type succinimide
compound represented by the following general formula (IX) or a
bis-type succinimide compound represented by the following general
formula (X):
##STR00016##
[0081] In the above general formulas (IX) and (X), R.sup.19,
R.sup.21 and R.sup.24 each represent an alkenyl or alkyl group
having a number-average molecular weight of 500 to 4,000. The
groups R.sup.21 and R.sup.24 may be the same or different. The
number-average molecular weight of R.sup.19, R.sup.21 and R.sup.24
is preferably from 1,000 to 4,000.
[0082] When the number-average molecular weight of R.sup.19,
R.sup.21 and R.sup.24 is 500 or more, the solubility of the
compound in the base oil is good. When the number-average molecular
weight is 4,000 or less, there is no fear of deterioration of the
dispersancy.
[0083] In the formulas, R.sup.20, R.sup.22 and R.sup.23 each
represent a C.sub.2 to C.sub.5 alkylene group. The groups R.sup.22
and R.sup.23 may be the same or different. The symbol r is an
integer of 1 to 10, s is 0 or an integer of 1 to 10. The symbol r
is preferably 2 to 5, more preferably 3 or 4. When r is 1 or more,
good dispersancy may be obtained. When r is 10 or less, the
compound exhibits good solubility in the base oil.
[0084] Further, in the general formula (X), s is preferably 1 to 4,
more preferably 2 or 3. The symbol s that lies within the
above-specified range is preferred for reasons of the dispersancy
and solubility in the base oil.
[0085] Examples of the alkenyl group include a polybutenyl group, a
polyisobutenyl group and an ethylene-propylene copolymer group.
Examples of the alkyl group include those which are obtained by
hydrogenating these alkenyl groups. Typical examples of the
suitable alkenyl group include a polybutenyl group and a
polyisobutenyl group. The polybutenyl group may be obtained by
polymerizing a mixture of 1-butene and isobutene, or high-purity
isobutene.
[0086] Typical examples of the suitable alkyl group include those
which are obtained by hydrogenating a polybutenyl group and a
polyisobutenyl group.
[0087] The above alkenylsuccinimide compound or alkylsuccinimide
compound may be generally produced by reacting a polyamine with an
alkenylsuccinic anhydride obtained by reaction of a polyolefin with
maleic anhydride, or with an alkylsuccinic anhydride, obtained by
hydrogenating the alkenylsuccinic anhydride. Also, the above
mono-type succinimide compound or bis-type succinimide compound may
be produced by varying a reaction ratio between the alkenylsuccinic
anhydride or alkylsuccinic anhydride and the polyamine.
[0088] As an olefin monomer from which the above polyolefin is
formed, there may be used a C.sub.2 to C.sub.8 .alpha.-olefin or a
mixture of two or more thereof. Among them, a mixture of isobutene
and butene-1 may be suitably used.
[0089] Examples of the polyamine include primary diamines such as
ethylenediamine, propylenediamine, butylenediamine and
pentylenediamine; polyalkylene polyamines such as
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, di(methylethylene)triamine,
dibutylenetriamine, tributylenetetramine and
pentapentylenehexamine; and piperazine derivatives such as
aminoethylpiperazine.
[0090] In addition to the above alkenyl or alkylsuccinimide
compound, there may also be used boron derivatives thereof and/or
organic acid-modified products thereof as the ashless
dispersant.
[0091] The boron derivatives of the alkenyl- or alkylsuccinimide
compound may be produced by an ordinary method. For example, the
boron derivatives may be produced by first reacting the above
polyolefin with maleic anhydride to obtain an alkenylsuccinic
anhydride, and then reacting the resulting alkenylsuccinic
anhydride with an intermediate product obtained by reacting the
above polyamine with a boron compound, such as boron oxide, a boron
halide, boric acid, boric anhydride, a boric acid ester and an
ammonium salt of orthoboric acid, to imidize the alkenylsuccinic
anhydride.
[0092] The content of boron in the boron derivatives is not
particularly limited, and is preferably in the range of 0.05% to 5%
by mass, more preferably 0.1% to 3% by mass, in terms of boron
element.
[0093] The compounding amount of the ashless dispersant is
preferably 0.5% to 15% by mass, more preferably 1% to 10% by mass,
still more preferably 3 to 7% by mass, based on a total amount of
the lubricating oil composition.
[0094] When the compounding amount is less than 0.5% by mass, the
effect on base number retaining property at high temperatures is
small. When the compounding amount exceeds 15% by mass, the
fluidity at low temperatures of the lubricating oil composition is
considerably deteriorated. Thus, either case is not preferable.
[0095] As the above-mentioned metallic detergent, there may be used
any alkaline earth metal-based detergents which are employed for
ordinary lubricating oils. Examples of the alkaline earth
metal-based detergent include alkaline earth metal sulfonates,
alkaline earth metal phenates, alkaline earth metal salicylates and
mixtures of two or more thereof.
[0096] As the alkaline earth metal sulfonates, there may be
mentioned alkaline earth metal salts of an alkyl aromatic sulfonic
acid obtained by sulfonating an alkyl aromatic compound having a
molecular weight of 300 to 1,500, preferably 400 to 700. Among
them, magnesium salts and/or calcium salts, especially calcium
salts are preferred.
[0097] As the alkaline earth metal phenates, there may be mentioned
alkaline earth metal salts of alkylphenols, alkylphenol sulfides
and Mannich reaction products of alkylphenols. Among them,
magnesium salts and/or calcium salts, especially calcium salts are
preferred.
[0098] As the alkaline earth metal salicylates, there may be
mentioned alkaline earth metal salts of alkyl salicylic acids.
Among them magnesium salts and/or calcium salts, especially calcium
salts are preferred.
[0099] The alkyl group contained in the compounds constituting the
above alkaline earth metal-based detergents is preferably a C.sub.4
to C.sub.30 alkyl group, more preferably a C.sub.6 to C.sub.18
linear or branched alkyl group. These alkyl groups may be straight
chained or branched.
[0100] These alkyl groups may be primary alkyl groups, secondary
alkyl groups or tertiary alkyl groups.
[0101] As the alkaline earth metal sulfonates, alkaline earth metal
phenates and alkaline earth metal salicylates, there may be used
neutral alkaline earth metal sulfonates, neutral alkaline earth
metal phenates and neutral alkaline earth metal salicylates which
may be produced by directly reacting the above alkyl aromatic
sulfonic acids, alkylphenols, alkylphenol sulfides, Mannich
reaction products of alkylphenols, alkyl salicylic acids or the
like with an alkaline earth metal base such as an oxide or a
hydroxide of an alkaline earth metal such as magnesium and/or
calcium or which may be produced by once forming an alkali metal
salt thereof and then converting the alkali metal salt into an
alkaline earth metal salt. Further, there may also be used basic
alkaline earth metal sulfonates, basic alkaline earth metal
phenates and basic alkaline earth metal salicylates which may be
produced by heating neutral alkaline earth metal sulfonates,
neutral alkaline earth metal phenates and neutral alkaline earth
metal salicylates together with an excess amount of an alkaline
earth metal salt or an alkaline earth metal base in the presence of
water. Furthermore, there may also be used perbasic alkaline earth
metal sulfonates, perbasic alkaline earth metal phenates and
perbasic alkaline earth metal salicylates which may be produced by
reacting neutral alkaline earth metal sulfonates, neutral alkaline
earth metal phenates and neutral alkaline earth metal salicylates
with an alkaline earth metal carbonate or an alkaline earth metal
borate in the presence of carbon dioxide.
[0102] The metallic detergent used in the present invention is
preferably an alkaline earth metal salicylate or alkaline earth
phenate, especially a perbasic salicylate or perbasic phenate, for
reasons of reducing a sulfur content of the composition.
[0103] The total base number of the metallic detergent used in the
present invention is preferably 10 to 500 mg KOH/g, more preferably
15 to 450 mg KOH/g. The metallic detergent may be selected from
these detergents and used singly or in combination of two or more
thereof.
[0104] The term "total base number" as used herein means the value
as measured by a potentiometric titration method (base
number/perchlorate method) according to the Item 7 of JIS K 2501
"Petroleum Products and Lubricants-Neutralization Number Testing
Method."
[0105] The metal ratio of the metallic detergent used in the
present invention is not specifically limited. The metallic
detergent having a metal ratio of 20 or less may be generally used
singly or as a mixture of two or more thereof. The metallic
detergent having a metal ratio of preferably 3 or less, more
preferably 1.5 or less, still more preferably 1.2 or less, is
particularly suitably used for reasons of further improved
oxidation stability, base number retaining property,
high-temperature detergency, etc.
[0106] Meanwhile, the term "metal ratio" as used herein means a
ratio represented by the formula: (valence of a metal
element).times.(content (mol %) of the metal element)/(content (mol
%) of a soap group) wherein the metal element is calcium,
magnesium, etc., and the soap group is a sulfonic group, a phenol
group, a salicylic group, etc.
[0107] The compounding amount of the metallic detergent is
preferably 0.01% to 20% by mass, more preferably 0.1% to 10% by
mass, still more preferably 0.5% to 5% by mass, based on the total
amount of the lubricating oil composition.
[0108] A compounding amount of the metallic detergent less than
0.01% by mass is not preferable because performances such as high
temperature detergency, oxidation stability and base number
retaining property are not easily obtainable. When the amount of
the metallic detergent compounded is 20% by mass or less, an effect
proportional to the compounding amount of the metallic detergent
may be generally obtained. In spite of the above specified range,
however, it is important that the upper limit of the compounding
amount of the metallic detergent should be as low as possible. By
so doing, the metal content, namely sulfuric acid ash content, of
the lubricating oil composition is reduced, with the result that
the exhaust gas purification device of automobiles is prevented
from being deteriorated.
[0109] The metallic detergent may be used singly or in combination
of two or more thereof as long as the content thereof lies within
the above-specified range.
[0110] Specifically, among the above-mentioned metallic detergents,
perbasic calcium salicylate and perbasic calcium phenate are
particularly preferred. Among the above-mentioned ashless
dispersants, the above-mentioned bis-polybutenylsuccinimide is
particularly preferred. Meanwhile, it is preferred that perbasic
calcium salicylate and perbasic calcium phenate each have a total
base number of 100 to 500 mgKOH/g, more preferably 200 to 500
mgKOH/g.
[0111] As the above-mentioned viscosity index improver, there may
be mentioned, for example, polymethacrylates, dispersion type
polymethacrylates, olefin-based copolymers (such as
ethylene-propylene copolymers), dispersion type olefin-based
copolymers and styrene-based copolymers (such as styrene-diene
copolymers and styrene-isoprene copolymers).
[0112] The compounding amount of the viscosity index improver is
preferably 0.5% to 15% by mass, more preferably 1% to 10% by mass,
based on the total amount of the lubricating oil composition from
the standpoint of effects attained by addition thereof.
[0113] As the above-mentioned pour point depressant, there may be
mentioned, for example, polymethacrylates having a weight-average
molecular weight of about 5,000 to about 50,000.
[0114] The compounding amount of the pour point depressant is
generally 0.1% to 2% by mass, more preferably 0.1% to 1% by mass,
based on the total amount of the lubricating oil composition from
the standpoint of effects attained by addition thereof.
[0115] As the metal deactivator, there may be mentioned, for
example, benzotriazole-based compounds, tolyl triazole-based
compounds, thiadiazole-based compounds and imidazole-based
compounds.
[0116] The compounding amount of the metal deactivator is
preferably 0.01% to 3% by mass, more preferably 0.01% to 1% by
mass, based on the total amount of the lubricating oil
composition.
[0117] As the rust inhibitor, there may be mentioned, for example,
petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene
sulfonates, alkenylsuccinic acid esters and polyhydric alcohol
esters.
[0118] The compounding amount of the rust inhibitor is preferably
0.01% to 1% by mass, more preferably 0.05% to 0.5% by mass, based
on the total amount of the lubricating oil composition from the
standpoint of effects attained by addition thereof.
[0119] As the above-mentioned defoaming agent, there may be
mentioned, for example, silicone oils, fluorosilicone oils and
fluoroalkyl ethers. The compounding amount of the defoaming agent
is preferably 0.005% to 0.5% by mass, more preferably 0.01% to 0.2%
by mass, based on the total amount of the lubricating oil
composition from the standpoint of a balance between the defoaming
effect and economy.
[0120] The lubricating oil composition of the present invention may
further contain a friction modifier, an anti-wear agent and an
extreme pressure agent, if necessary. The friction modifier herein
is a compound other than the polar group-containing compounds which
are an essential ingredient of the present invention. The
compounding amount of the friction modifier agent is preferably
0.01% to 2% by mass, more preferably 0.01% to 1% by mass or less,
based on the total amount of the lubricating oil composition.
[0121] As the anti-wear agent or the extreme-pressure agent, there
may be mentioned sulfur containing compounds such as zinc
dithiophosphate, zinc phosphate, zinc dithiocarbamate, molybdenum
dithiocarbamate, molybdenum dithiophosphate, disulfides (other than
the sulfur-containing compounds of the general formula (I) or (II)
used in the present invention; dibenzyldisulfide is an example
thereof), sulfurized olefins, sulfurized oils and fats, sulfurized
esters, thiocarbonates, thiocarbamates and polysulfides; phosphorus
containing compounds such as phosphorous acid esters, phosphoric
acid esters, phosphonic acid esters and amine salts or metal salts
of these esters; and sulfur- and phosphorus-containing anti-wear
agents such as thiophosphorous acid esters, thiophosphoric acid
esters, thiophosphonic acid esters and amine salts or metal salts
of these esters.
[0122] The compounding amount of the anti-wear agent or the
extreme-pressure agent to be compounded should be such that the
phosphorus content, sulfur content and metal content of the
lubricating oil are not excessively large by addition thereof.
[0123] The lubricating oil composition of the present invention may
be formulated as described in the foregoing and preferably has the
following properties:
[0124] (1) the sulfuric acid ash content (JIS K 2272) is 0.6% by
mass or less, more preferably 0.1% by mass or less; and
[0125] (2) the phosphorus content (JPI-5S-38-92) is 0.5% by mass or
less, more preferably 0% by mass.
[0126] Additionally, it is more preferred that the following
properties are met:
[0127] (3) the sulfur content (JIS K 2541) is 0.4% by mass or less,
more preferably 0.2% by mass or less; and
[0128] (4) the boron content is 0.4% by mass or less, more
preferably 0.2% by mass or less.
[0129] The lubricating oil composition of the present which
satisfies the above properties can suppress deterioration of an
oxidation catalyst, a three way catalyst, an NOx occlusion
reduction catalyst, a diesel particulate filter (DPF), etc. which
are used in automobile engines.
[0130] The lubricating oil composition of the present invention
uses a combination of the above-described sulfur-containing
compound and the polar group-containing compound. As a result of
such combined use, there are achieved wear resisting and friction
reducing effects which are far superior to those attained by
separate use thereof. Accordingly, even when zinc dithiophosphate
which has been hitherto often used as a lubricant oil additive is
not used, the lubricating oil composition shows sufficiently
excellent lubricating performance and makes it possible to achieve
properties of low sulfuric acid ash, etc. Furthermore, the
lubricating oil composition of the present invention exhibits
excellent friction reducing effect even when used for a DLC-treated
sliding part as described hereinafter.
[0131] The lubricating oil composition of the present invention can
be suitably used as a lubricant oil for use in an internal
combustion engine, such as a gasoline engine, a diesel engine or a
gas engine, for two-wheeled vehicles, four-wheeled vehicles, power
generators, ships or the like, and is particularly suited for
internal combustion engines equipped with an exhaust gas
purification device because of its low phosphorus content, low
sulfur content and low sulfuric acid ash content.
[0132] The lubricating oil composition of the present invention is
also suitably used for applications other than those described
above. Especially, since the lubricating oil composition of the
present invention shows excellent wear resistance and friction
reducing effect, it can be used for lubrication of internal
combustion engines, automatic transmissions, continuously variable
transmissions, manual transmissions, power steerings, shock
absorbers, compressors, cooling medium compressors, refrigerators,
hydraulic pumps and clutch pulleys. Namely, the lubricating oil
composition of the present invention may be used as internal
combustion engine oils, automatic transmission oils, continuously
variable transmission oils, manual transmission oils, power
steering oils, shock absorber oils, compressor oils, refrigerator
oils, hydraulic pump oils and clutch pulley lubricating oils and
greases.
[0133] The lubricating oil composition of the present invention
exhibits friction reducing effect and excellent wear resistance not
only for a sliding surface of a metal such as a steel but also for
a sliding surface having a DLC film on at least a portion
thereof.
[0134] It is preferred that the hydrogen content of such a DLC be
40% by atom or less, more preferably 30% by atom or less,
particularly preferably 20% by atom or less.
[0135] A counter member with which the sliding surface of such a
DLC film-bearing member is to be brought into contact is not
specifically limited and may be, for example, an iron or iron alloy
member, aluminum alloy member or an organic material such as a
resin or rubber material.
EXAMPLES
[0136] The present invention will be next described in more detail
by way of Examples and Comparative Examples. The scope of the
present invention, however, is not limited to these examples in any
way.
Methods for Measuring Properties and Performances:
[0137] The properties and performances of the lubricating oil
compositions obtained in the following Examples and Comparative
Examples are measured by the methods shown below.
(1) Kinematic Viscosity:
[0138] Measured according to JIS K 2283.
(2) Phosphorus Content:
[0139] Measured according to JPI-5S-38-92.
(3) Sulfur Content:
[0140] Measured according to JIS K 2541.
(4) Boron Content:
[0141] Measured according to JPI-5S-38-92.
(5) Sulfuric Acid Ash Content:
[0142] Measured according to JIS K 2272.
(6) Reciprocating Friction Test
[0143] The test was carried out with a reciprocating friction
tester to determine a friction coefficient using a test plate and a
test ball shown below under the conditions shown below.
Test plate: SUJ-2 plate Test ball: SUJ-2 ball (1/2 in) treated with
DLC (hydrogen content: 20%)
--Test Conditions--
[0144] Testing temperature: 100.degree. C.
[0145] Load: 200 g
[0146] Amplitude: 10 mm
[0147] Sliding speed: 1.0 mm/sec
(7) Frictional Wear Test
[0148] The test was carried out with a reciprocating friction
tester to determine wear track length using a test plate and a test
ball shown below under the conditions shown below.
Test plate: SUJ-2 plate Test ball: SUJ-2 ball (10 mm diameter)
--Test Conditions--
[0149] Testing temperature: 100.degree. C.
[0150] Load: 200 N
[0151] Amplitude: 10 mm
[0152] Frequency: 10 Hz
[0153] Testing time: 30 min
Examples 1 to 7 and Comparative Examples 1 to 9
[0154] The base oil and additives shown in Table 1 were blended in
the proportion shown in Table 1 to prepare lubricating oil
compositions. The properties, formulations and performances of the
compositions are also shown in Table 1.
TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 Formulation Base oil
88.60 88.60 88.60 88.60 88.60 88.60 87.80 Composition
Sulfur-containing compound A 0.40 0.40 0.40 0.40 0.40 0.40 -- (% by
mass) Sulfur-containing compound B -- -- -- -- -- -- 1.20 Polar
group-containing compound A 0.50 -- -- -- -- -- 0.50 Polar
group-containing compound B -- 0.50 -- -- -- -- -- Polar
group-containing compound C -- -- 0.50 -- -- -- -- Polar
group-containing compound D -- -- -- 0.50 -- -- -- Polar
group-containing compound E -- -- -- -- 0.50 -- -- Polar
group-containing compound F -- -- -- -- -- 0.50 -- Viscosity index
improver 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Pour point depressant
0.30 0.30 0.30 0.30 0.30 0.30 0.30 Polybutenylsuccinimide 4.00 4.00
4.00 4.00 4.00 4.00 4.00 Phenol-based antioxidant 0.50 0.50 0.50
0.50 0.50 0.50 0.50 Amine-based antioxidant 0.50 0.50 0.50 0.50
0.50 0.50 0.50 Zinc dialkyldithiophosphate -- -- -- -- -- -- --
Etc. 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Total 100.00 100.00 100.00
100.00 100.00 100.00 100.00 Properties Phosphorus content (% by
mass) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Sulfur content (% by mass)
0.1 0.1 0.1 0.1 0.1 0.1 0.1 Boron content (% by mass) 0.08 0.08
0.08 0.08 0.08 0.08 0.08 Sulfuric acid ash content (% by mass) 0.05
0.05 0.05 0.05 0.05 0.05 0.05 Reciprocating friction test (friction
coefficient) 0.115 0.117 0.113 0.110 0.116 0.117 0.114 Frictional
wear test (wear track diameter; mm) 0.46 0.45 0.45 0.44 0.42 0.43
0.45
TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 4 5 6 7 8 9
Formulation Base oil 89.10 89.00 89.00 89.00 89.00 89.00 89.00
88.40 87.90 Composition Sulfur-containing 0.40 -- -- -- -- -- -- --
-- (% by mass) compound A Polar group-containing -- 0.50 -- -- --
-- -- -- -- compound A Polar group-containing -- -- 0.50 -- -- --
-- -- -- compound B Polar group-containing -- -- -- 0.50 -- -- --
-- -- compound C Polar group-containing -- -- -- -- 0.50 -- -- --
-- compound D Polar group-containing -- -- -- -- -- 0.50 -- -- --
compound E Polar group-containing -- -- -- -- -- -- 0.50 0.50 0.50
compound F Viscosity index improver 5.00 5.00 5.00 5.00 5.00 5.00
5.00 5.00 5.00 Pour point depressant 0.30 0.30 0.30 0.30 0.30 0.30
0.30 0.30 0.30 Polybutenylsuccinimide 4.00 4.00 4.00 4.00 4.00 4.00
4.00 4.00 4.00 Phenol-based antioxidant 0.50 0.50 0.50 0.50 0.50
0.50 0.50 0.50 0.50 Amine-based antioxidant 0.50 0.50 0.50 0.50
0.50 0.50 0.50 0.50 0.50 Zinc -- -- -- -- -- -- -- 0.60 0.60
dialkyldithiophosphate Etc. 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
0.20 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
100.00 Properties Phosphorus content 0.00 0.00 0.00 0.00 0.00 0.00
0.00 0.05 0.05 (% by mass) Sulfur content (% by mass) 0.1 0.0 0.0
0.0 0.0 0.0 0.0 0.1 0.1 Boron content (% by mass) 0.08 0.08 0.08
0.08 0.08 0.08 0.08 0.08 0.08 Sulfuric acid ash content 0.05 0.05
0.05 0.05 0.05 0.05 0.05 0.17 0.17 (% by mass) Reciprocating
friction test 0.140 0.125 0.128 0.124 0.125 0.126 0.124 0.155 0.143
(friction coefficient) Frictional wear test (wear track diameter;
0.52 0.64 0.65 0.63 0.63 0.60 0.61 0.48 0.50 mm) Note: Base oil:
Hydrogenated refined base oil (kinematic viscosity at 40.degree.
C.: 21 mm.sup.2/s; kinematic viscosity at 100.degree. C.: 4.5
mm.sup.2/s; viscosity index: 127; % C.sub.A: 0.0; sulfur content:
less than 20 ppm by mass; NOACK test evaporation amount: 13.3% by
mass) Sulfur-containing compound A: 1,1-bis(octoxycarbonylmethyl)
disulfide Sulfur-containing compound B: Tetra-1-hexyl dithiomalate
Polar group-containing compound A: Glycerol monoolate Polar
group-containing compound B: Oleic acid diethanolamide Polar
group-containing compound C: Glycerol monooleyl ether Polar
group-containing compound D: N,N-Dipolyoxyethylene-N-oleylamine
Polar group-containing compound E: Reaction product between
glycerol monoolate and boric acid Polar group-containing compound
F: Reaction product between oleic acid diethanolamide and boric
acid Viscosity index improver: Polymethacrylate (weight average
molecular weight: 420,000; resin content: 39% by mass) Pour point
depressant: Polyalkyl methacrylate (weight average molecular
weight: 6,000) Polybutenylsuccinimide: Number-average molecular
weight of polybutenyl group: 1,000; Nitrogen content: 1.76% by
mass; Boron content: 1.9% by mass Phenol-based antioxidant:
Octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate Amine-based
antioxidant: Dialkyldiphenylamine (nitrogen content: 4.62% by mass)
Zinc dialkyldithiophosphate (Zn content: 9.0% by mass, phosphorus
content: 8.2% by mass, sulfur content: 17.1% by mass, alkyl group:
mixture of secondary butyl group and secondary hexyl group) Etc.:
Defoaming agent and metal deactivator
[0155] As shown in Tables 1 and 2, the lubricating oil compositions
of Examples 1 to 7 gives low friction coefficients and small wear
track diameters due to the synergetic effect of the combined use of
the sulfur-containing compound and the polar group-containing
compound.
[0156] Namely, in Comparative Example 1 which does not use a polar
group-containing compound, the friction coefficient is 0.140. In
Comparative Examples 2 to 7 which do not use a sulfur-containing
compound, the friction coefficient is 0.124 to 0.128. However, when
these compounds are used in combination, the friction coefficient
can be reduced to 0.110 to 0.117 (Examples 1 to 7). Similarly,
although Comparative Example 1 which does not use a polar
group-containing compound gives a wear track diameter of 0.52 and
Comparative Examples 2 to 7 which do not use a sulfur-containing
compound give a wear track diameter of 0.60 to 0.65, the wear track
diameter can be reduced to 0.42 to 0.46 by using these compounds in
combination (Examples 1 to 7).
[0157] Also, it will be appreciated by comparison between Examples
1 to 7 and Comparative Example 8 that the effect achieved by the
combined use of the additives according to the present invention is
superior to the effect attained by using zinc
dialkyldithiophosphate alone. Further, as will be appreciated from
the results in Comparative Example 9, when the zinc
dialkyldithiophosphate is substituted for the sulfur-containing
compound of the present invention and is used in combination with
the polar group-containing compound, it is impossible to obtain
such a low friction coefficient and a small wear track diameter as
attained in Examples 1 to 7.
[0158] As described in the foregoing, the combined use of the
specific sulfur-containing compound and the specific polar
group-containing compound can make it possible to obtain higher
wear resistance than that attained by the zinc
dialkyldithiophosphate. Consequently, it is possible to provide a
lubricating oil composition which is excellent in wear resistance,
despite its low phosphorus content, low sulfur content and low
sulfuric acid ash content, and which exhibits excellent friction
reducing effect.
INDUSTRIAL APPLICABILITY
[0159] According to the present invention there is provided a
lubricating oil composition which is excellent in wear resistance,
despite its low phosphorus content, low sulfur content and low
sulfuric acid ash content, and which exhibits excellent friction
reducing effect even when used for a DLC-treated sliding part. The
lubricating oil composition according to the present invention,
therefore, can be particularly suitably used as a lubricating oil
composition for internal combustion engines such as gasoline
engines, diesel engines and gas engines.
* * * * *