U.S. patent application number 16/310503 was filed with the patent office on 2019-08-29 for lubricant additive composition, lubricating composition containing same and engine oil composition consisting of lubricating com.
This patent application is currently assigned to ADEKA CORPORATION. The applicant listed for this patent is ADEKA CORPORATION. Invention is credited to Shinji IINO, Eiji KATSUNO, Taro SUMI.
Application Number | 20190264125 16/310503 |
Document ID | / |
Family ID | 60785990 |
Filed Date | 2019-08-29 |
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United States Patent
Application |
20190264125 |
Kind Code |
A1 |
IINO; Shinji ; et
al. |
August 29, 2019 |
LUBRICANT ADDITIVE COMPOSITION, LUBRICATING COMPOSITION CONTAINING
SAME AND ENGINE OIL COMPOSITION CONSISTING OF LUBRICATING
COMPOSITION
Abstract
A lubricant additive composition including, as a component (A),
an organic molybdenum compound represented by general formula (1)
described in the specification, and as a component (B), an amine
compound represented by general formula (2) described in the
specification, wherein content of the component (B) is 1 to 20
parts by mass relative to 100 parts by mass of molybdenum atoms of
the component (A), and a lubricating composition containing
same.
Inventors: |
IINO; Shinji; (Tokyo,
JP) ; KATSUNO; Eiji; (Tokyo, JP) ; SUMI;
Taro; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ADEKA CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
ADEKA CORPORATION
Tokyo
JP
|
Family ID: |
60785990 |
Appl. No.: |
16/310503 |
Filed: |
June 27, 2017 |
PCT Filed: |
June 27, 2017 |
PCT NO: |
PCT/JP2017/023621 |
371 Date: |
December 17, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 141/12 20130101;
C10M 2207/262 20130101; C10N 2010/04 20130101; C10M 2227/00
20130101; C10M 2219/066 20130101; C10N 2040/252 20200501; C10M
2215/28 20130101; C10M 169/04 20130101; C10N 2030/10 20130101; C10N
2010/12 20130101; C10M 2215/086 20130101; C10M 2223/045 20130101;
C10M 141/08 20130101; C10M 2207/144 20130101; C10M 2207/284
20130101; C10N 2030/12 20130101; C10M 2215/223 20130101; C10M
2227/061 20130101; C10N 2030/06 20130101; C10M 135/18 20130101;
C10M 2219/068 20130101; C10N 2040/25 20130101; C10M 133/06
20130101; C10M 2215/04 20130101; C10M 2203/1006 20130101; C10M
139/00 20130101; C10M 2219/046 20130101; C10N 2040/255
20200501 |
International
Class: |
C10M 141/12 20060101
C10M141/12; C10M 169/04 20060101 C10M169/04; C10M 135/18 20060101
C10M135/18; C10M 139/00 20060101 C10M139/00; C10M 133/06 20060101
C10M133/06 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 29, 2016 |
JP |
2016-128713 |
Claims
1. A lubricant additive composition comprising, as a component (A),
an organic molybdenum compound represented by the following general
formula (1), and as a component (B), an amine compound represented
by the following general formula (2), wherein content of the
component (B) is 1 to 20 parts by mass relative to 100 parts by
mass of molybdenum atoms of the component (A): ##STR00005## wherein
R.sup.1 to R.sup.4 respectively represent an alkyl group having 1
to 18 carbon atoms, and X.sup.1 to X.sup.4 respectively represent
an oxygen atom or a sulphur atom; ##STR00006## wherein R.sup.5 and
R.sup.6 respectively represent an alkyl group having 1 to 18 carbon
atoms or an alkenyl group having 2 to 18 carbon atoms.
2. A lubricating composition comprising a base oil, and the
lubricant additive composition according to claim 1.
3. The lubricating composition according to claim 2, further
comprising, as a component (C), an alkaline earth metal
salicylate.
4. The lubricating composition according to claim 2, further
comprising, as a component (D), an alkenyl succinimide
dispersant.
5. The lubricating composition according to claim 2, further
comprising, as a component (E), a phenolic antioxidant.
6. The lubricating composition according to claim 2, further
comprising, as a component (F), a zinc dithiophosphate represented
by the following general formula (3): ##STR00007## wherein R.sup.7
to R.sup.10 respectively represent an alkyl group having 3 to 14
carbon atoms.
7. The lubricating composition according to claim 2, further
comprising, as a component (G), at least one ashless friction
regulator selected from the group consisting of polyhydric alcohol
fatty acid partial esters, (poly)glycerol alkyl ethers, alkyl
alkanolamines, alkenyl alkanolamines and fatty acid
alkanolamides.
8. An engine oil composition consisting of the lubricating
composition according to claim 1.
9. A method for suppressing corrosion of a copper component of a
machine and improving lubrication ability by adding, to a base oil
used for a lubricating composition, an organic molybdenum compound
represented by the following general formula (1) and an amine
compound represented by the following general formula (2), wherein
the amine compound is added at 1 to 20 parts by mass relative to
100 parts by mass of molybdenum atoms of the organic molybdenum
compound: ##STR00008## wherein R.sup.1 to R.sup.4 respectively
represent an alkyl group having 1 to 18 carbon atoms, and X.sup.1
to X.sup.4 respectively represent an oxygen atom or a sulphur atom;
##STR00009## wherein R.sup.5 and R.sup.6 respectively represent an
alkyl group having 1 to 18 carbon atoms or an alkenyl group having
2 to 18 carbon atoms.
Description
TECHNICAL FIELD
[0001] The present invention relates to a lubricant additive
composition containing an organic molybdenum compound, a
lubricating composition containing the lubricant additive
composition and an engine oil consisting of the lubricating
composition.
BACKGROUND ART
[0002] Reductions in automobile fuel consumption initiated due to
the oil crisis is a very important issue in view of resource
protection and environmental protection. Automotive fuel
consumption has been improved by reduction of the body weight of
automobiles, improvements in engine combustion and reduction of
friction in engines and power trains. Engine friction has been
reduced by, for example, improvement in valve system mechanisms,
reduction of surface roughness of sliding members and use of
fuel-efficient engine oil. In order to reduce fuel consumption by
engine oil, reduction of viscosity aimed at reducing friction loss
under fluid lubrication conditions in piston systems and bearing
members has been studied, and addition of friction reducing agents
aimed at reducing friction loss under mixed lubrication and
boundary lubrication in valve systems have been proposed.
[0003] Organic molybdenum compounds containing sulphur such as
molybdenum dialkyldithiocarbamate and molybdenum
dialkyldithiophosphate have the excellent effect of friction
reduction, and thus are widely used for engine lubricating oil and
the like. However, the effect of friction reduction only by
increasing the amount of organic molybdenum compounds added has
limitations, and an increase in the amount of organic molybdenum
compounds added causes problems such as generation of deposits due
to precipitated or deteriorated organic molybdenum compounds. In
order to improve the effect of the organic molybdenum compound, use
of lubricating oil compositions containing an organic molybdenum
compound and an ashless friction regulator, for example lubricating
oil compositions containing an organic molybdenum compound and a
polyhydric alcohol fatty acid partial ester (for example, see
Patent Documents 1 to 3) or an alkyl alkanolamine or fatty acid
alkanolamide (for example, see Patent Documents 4 and 5) have been
studied.
[0004] It is believed that organic molybdenum compounds containing
sulphur are decomposed on sliding surfaces to form films similar to
molybdenum disulphide, which films reduce friction. Therefore,
lubricating oil compositions (for example, see Patent Documents 6
and 7) containing an organic molybdenum compound containing sulphur
and tetrabenzyl thiuram disulphide have been studied and it is
thought that in order to increase solubility of tetrabenzyl thiuram
disulphide, an amine compound is effective (for example, see Patent
Document 7). However, in order to dissolve tetrabenzyl thiuram
disulphide in abase oil, a high amount of amine compound is
required and copper components of machines made of copper or copper
alloys are corroded in some cases.
CITATION LIST
Patent Documents
[0005] [Patent Document 1] Japanese Patent Application Publication
No. H05-279686
[0006] [Patent Document 2] Japanese Patent Application Publication
No. H08-067890
[0007] [Patent Document 3] Japanese Patent Application Publication
No. 2005-082709
[0008] [Patent Document 4] Japanese Patent Application Publication
No. H07-150173
[0009] [Patent Document 5] Japanese Patent Application Publication
No. 2003-221588
[0010] [Patent Document 6] Japanese Patent Application Publication
No. 2012-197393
[0011] [Patent Document 7] Japanese Patent Application Publication
No. 2013-119597
SUMMARY OF INVENTION
Technical Problem
[0012] The level of reduction in automobile fuel consumption being
sought has recently increased, and there is a need for an engine
oil having further reduced friction. In addition, a lubricant
having an improved effect of friction reduction for other machines
is also expected. Therefore, an issue to be addressed by the
present invention is to further improve the effect of friction
reduction by an organic molybdenum compound.
Solution to Problem
[0013] The inventors of the present invention carried out extensive
studies in order to solve the above problem and, as a result, found
that by adding a small amount of dialkylamine to an organic
molybdenum compound containing sulphur, the effect of friction
reduction by the organic molybdenum compound is increased without
corrosion of copper or copper alloys. The inventors thereby
completed the present invention. Namely, the present invention
pertains to a lubricant additive composition containing, as a
component (A), an organic molybdenum compound represented by the
following general formula (1), and as a component (B), an amine
compound represented by the following general formula (2), wherein
content of the component (B) is 1 to 20 parts by mass relative to
100 parts by mass of molybdenum atoms derived from the component
(A):
##STR00001##
[0014] wherein R.sup.1 to R.sup.4 respectively represent an alkyl
group having 1 to 18 carbon atoms, and X.sup.1 to X.sup.4
respectively represent an oxygen atom or a sulphur atom;
##STR00002##
[0015] wherein R.sup.5 and R.sup.6 respectively represent an alkyl
group having 1 to 18 carbon atoms or an alkenyl group having 2 to
18 carbon atoms.
Advantageous Effects of Invention
[0016] By adding to an organic molybdenum compound represented by
general formula (1) a dialkylamine represented by general formula
(2) at a specific ratio, the effect of friction reduction by the
organic molybdenum compound can be improved and corrosion of
components used in machines, particularly corrosion of copper and
copper alloys can be significantly prevented. Therefore, the
present invention can provide an advantageous lubricant additive
composition for lubricating compositions.
DESCRIPTION OF EMBODIMENTS
[0017] In the lubricant additive composition of the present
invention, the component (A) is an organic molybdenum compound
represented by general formula (1). In the general formula (1),
R.sup.1 to R.sup.4 respectively represent an alkyl group having 1
to 18 carbon atoms. Examples of the alkyl group having 1 to 18
carbon atoms include a methyl group, an ethyl group, a propyl
group, a butyl group, a pentyl group, a hexyl group, a heptyl
group, an octyl group, an isopropyl group, an isobutyl group, a
secondary butyl group, a tertiary butyl group (hereinafter
"tertiary" is abbreviated as "t"), an isopentyl group, a secondary
pentyl group, a t-pentyl group, a secondary hexyl group, a
secondary heptyl group, a secondary octyl group, a 2-ethylhexyl
group, a nonyl group, an isononyl group, a decyl group, a branched
decyl group, a dodecyl group, a tridecyl group, a branched tridecyl
group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a
heptadecyl group, an octadecyl group and the like. Because of
preferable solubility to mineral oil and hydrocarbon synthetic oil
and preferable thermal stability, R.sup.1 to R.sup.4 are
respectively preferably an alkyl group having 6 to 16 carbon atoms
and more preferably an alkyl group having 7 to 14 carbon atoms.
Branched alkyl groups are preferred to linear alkyl groups because
the molybdenum compound may have a lower melting point and may be
less deposited. R.sup.1 to R.sup.4 may be the same hydrocarbon
group or different hydrocarbon groups; however, it is preferable
that at least one of R.sup.1 to R.sup.4 is different from other
groups because the molybdenum compound may have a lower melting
point and may be less deposited, and it is more preferable that
R.sup.1 and R.sup.2 are the same and R.sup.3 and R.sup.4 are the
same and R.sup.1 and R.sup.3 are different because of industrial
availability. Specifically, the compound wherein R.sup.1 and
R.sup.2 are respectively 2-ethylhexyl and R.sup.3 and R.sup.4 are
respectively a branched tridecyl group, or R.sup.1 to R.sup.4 are
respectively 2-ethylhexyl is preferable and a compound wherein
R.sup.1 and R.sup.2 are respectively 2-ethylhexyl and R.sup.3 and
R.sup.4 are respectively a branched tridecyl group is more
preferable.
[0018] In general formula (1), X.sup.1 to X.sup.4 respectively
represent an oxygen atom or a sulphur atom. Because of excellent
lubricity, it is preferable that two to three of X.sup.1 to X.sup.4
are sulphur atoms and the rest are oxygen atom(s). For example, a
compound wherein X.sup.1 and X.sup.2 are respectively a sulphur
atom and X.sup.3 and X.sup.4 are respectively an oxygen atom is
preferred.
[0019] In the present invention, an organic molybdenum compound
(A1) wherein R.sup.1 and R.sup.2 are respectively 2-ethylhexyl and
R.sup.3 and R.sup.4 are respectively a branched tridecyl group; and
X.sup.1 and X.sup.2 are respectively a sulphur atom and X.sup.3 and
X.sup.4 are respectively an oxygen atom, and an organic molybdenum
compound (A2) wherein R.sup.1 to R.sup.4 are respectively
2-ethylhexyl; and X.sup.1 and X.sup.2 are respectively a sulphur
atom and X.sup.3 and X.sup.4 are respectively an oxygen atom are
preferred, and the organic molybdenum compound (A1) is more
preferred.
[0020] In the lubricant additive composition of the present
invention, the component (B) is an amine compound represented by
general formula (2). In the general formula (2), R.sup.5 and
R.sup.6 respectively represent an alkyl group having 1 to 18 carbon
atoms or an alkenyl group having 2 to 18 carbon atoms. Examples of
the alkyl group having 1 to 18 carbon atoms include alkyl groups
exemplified for R.sup.1 to R.sup.4 in the general formula (1).
Examples of the alkenyl group having 2 to 18 carbon atoms include a
vinyl group, a 1-methylethenyl group, a 2-methylethenyl group, a
propenyl group, a butenyl group, an isobutenyl group, a pentenyl
group, a hexenyl group, a heptenyl group, an octenyl group, a
decenyl group, a pentadecenyl group, an octadecenyl group and the
like. R.sup.5 and R.sup.6 maybe the same group or different groups;
however, it is preferable that R.sup.5 and R.sup.6 are the same
group because of industrial availability.
[0021] In the general formula (2), the sum of the carbon atoms of
R.sup.5 and R.sup.6 is preferably at least 8 and more preferably at
least 12 because when the amine compound has an extremely low
boiling point, the amine compound in the general formula (2) is
volatilized and eliminated during use.
[0022] Among the amine compounds represented by general formula
(2), dibutylamine, dipropylamine, dihexylamine, diheptylamine,
dioctylamine, bis(2-ethylhexyl)amine, dinonylamine,
diisononylamine, didecylamine, di-branched decylamine,
didodecylamine, di-branched tridecylamine, ditetradecylamine,
dihexadecylamine, dioctadecylamine are preferred because of
industrial availability, bis(2-ethylhexyl)amine, dinonylamine,
diisononylamine, didecylamine, di-branched decylamine,
didodecylamine, di-branched tridecylamine are more preferred
because of an increased effect of friction reduction, and bis
(2-ethylhexyl) amine and di-branched tridecylamine are still more
preferred.
[0023] In the present invention, the content of the component (B)
is 1 to 20 parts by mass relative to 100 parts by mass of
molybdenum atoms derived from the component (A). When the content
of the component (B) is less than 1 part by mass, the effect of
lubricity may not be sufficient, and when the content is more than
20 parts by mass, corrosion of copper or copper alloys may occur.
The component (B) is preferably 2 to 19 parts by mass, more
preferably 5 to 18 parts by mass and still more preferably 10 to 17
parts by mass relative to 100 parts by mass of molybdenum atoms
derived from the component (A).
[0024] The lubricant additive composition of the present invention
may consist of the component (A) and the component (B). However, in
view of handling and convenience upon use of the additive
composition of the present invention, the composition may be
dissolved in a base oil or may be in a package combined with other
lubricating oil additives. When the lubricant additive composition
of the present invention contains other components, the content of
the component (A) is preferably at least 1% by mass and more
preferably at least 20% by mass relative to the whole amount of the
lubricant additive composition.
[0025] The lubricant additive composition of the present invention
is added to a base oil or a base oil and a thickener to be used as,
respectively, a lubricating oil composition or a grease
composition. In the present invention, the lubricating oil
composition and the grease composition are collectively referred to
as a lubricating composition. Examples of the base oil include
mineral oils such as paraffin mineral oils, naphthene mineral oils
and purified mineral oils obtained by subjecting the above to
hydrogenation refining, solvent deasphalting, solvent extraction,
solvent dewaxing, hydrogenation dewaxing, contact dewaxing,
hydrogenolysis, alkali distilling, sulphuric acid cleaning or white
clay treatment; hydrocarbon synthetic oils such as
poly-.alpha.-olefins, ethylene-.alpha.-olefin copolymers,
polybutenes, GTL (Gas to liquids) base oils, alkylbenzenes and
alkylnaphthalenes; ether synthetic oils such as polyphenyl ethers,
alkyl-substituted diphenyl ethers and polyalkylene glycols; ester
synthetic oils such as polyol esters, dibasic acid esters, hindered
esters and monoesters; phosphate ester synthetic oils, polysiloxane
synthetic oils, and fluorinated hydrocarbon synthetic oils. The
base oils may be used alone or as a mixture of two or more. The
base oil for which the lubricant additive composition of the
present invention is used is preferably a mineral oil or a
hydrocarbon synthetic oil and more preferably a paraffin purified
mineral oil, a poly-.alpha.-olefin or a GTL base oil because the
effect of lubricity improvement by the component (A) may be easily
obtained.
[0026] Examples of the thickener used with the lubricant additive
composition of the present invention for a grease include soap or
complex soap thickeners, organic non-soap thickeners, inorganic
non-soap thickeners and the like. A grease made of abase oil and a
thickener and not containing other additives may be referred to as
a base grease. The consistency of the grease for which the
lubricant additive composition of the present invention is used may
vary according to the application of the grease and is not
particularly limited. The consistency is generally about 100 to
500, and the content of the thickener is generally about 5 to 20
parts by mass relative to 100 parts by mass of the base oil.
[0027] Examples of the soap thickener includes soaps obtained by
reaction of higher fatty acids such as lauric acid, myristic acid,
palmitic acid, stearic acid, 12-hydroxystearic acid, arachic acid,
behenic acid, zoomaric acid, oleic acid, linoleic acid, linolenic
acid and ricinoleic acid and bases such as lithium, sodium,
potassium, aluminium, barium and calcium, and complex soap
thickeners obtained by reaction of the fatty acids and the bases
above and acetic acid, benzoic acid, sebacic acid, azelaic acid,
phosphoric acid, boric acid or the like. Examples of the organic
non-soap thickener include terephtalate thickeners, urea
thickeners, fluorine thickeners such as polytetrafluoroethylene and
fluorinated ethylene-propylene copolymers and the like. Examples of
inorganic non-soap thickener include montmorillonite, bentonite,
silica aerogel, boron nitride and the like. Among the thickeners,
urea thickeners are preferable because the effect of friction
reduction by the component (B) is increased. Examples of the urea
thickener include monourea compounds obtained by reaction of
monoisocyanates and monoamines, diurea compounds obtained by
reaction of diisocyanates and monoamines, urea urethane compounds
obtained by reaction of diisocyanates, monoamines and monools,
tetraurea compounds obtained by reaction of diisocyanates, diamines
and monoisocyanates and the like.
[0028] In the lubricating composition of the present invention, an
extremely low content of the component (A) of the present invention
may cause an insufficient effect of friction reduction, and an
extremely high amount of addition may cause sludge and corrosion.
When the lubricating composition of the present invention is a
lubricating oil composition, the component (A) in terms of the
amount of molybdenum atoms is preferably 50 to 2000 ppm by mass,
more preferably 70 to 1500 ppm by mass and still more preferably 80
to 1000 ppm by mass relative to the whole amount of the lubricating
composition. When the lubricating composition of the present
invention is a grease composition, the amount of the component (A)
added in terms of the amount of molybdenum atoms is preferably 100
ppm by mass to 5% by mass, more preferably 150 ppm by mass to 3% by
mass and still more preferably 200 ppm by mass to 2% by mass
relative to the grease and the like.
[0029] Generally, the lubricating composition may contain, if
necessary, a metal-based cleaner, an ashless dispersant, an
antioxidant, an oiliness agent, an anti-wear agent, an extreme
pressure agent, a rust preventing agent, a metal deactivator, a
viscosity index improver, a pour point depressant, a solid
lubricant and the like.
[0030] [Metal-Based Cleaner]
[0031] Examples of the metal-based cleaner include alkaline earth
metal sulphonates, alkaline earth metal phenates, alkaline earth
metal phosphonates, alkaline earth metal salicylates, alkaline
earth metal naphthenates and the like, and examples of the alkaline
earth metal include magnesium, calcium, barium and the like. The
lubricating composition of the present invention preferably
contains, as a component (C), an alkaline earth metal salicylate
because of an increased effect of friction reduction by the
component (A) and calcium salicylate is preferred among others.
[0032] Metal-based cleaners having a total base number (TBN)
according to ASTM D2896 of 20 to 600 mgKOH/g are known. When the
TBN is extremely low, a high amount of metal-based cleaner must be
added, and when the TBN is extremely high, the lubricity of the
component (A) may be adversely affected. Metal-based cleaners
diluted with light lubricant base oil or the like are generally
marketed and are available. The TBN of the metal-based cleaner as
used in the present invention is a TBN of pure component without a
diluent such as light lubricant base oil. The component (C) has a
TBN of preferably 50 to 500 mgKOH/g and more preferably 100 to 450
mgKOH/g. Generally, a metal-based cleaner has an increased TBN by
including a carbonate salt of an alkaline earth metal, and the
component (C) of the present invention may contain a borate salt
instead of some of the carbonate salt.
[0033] When the content of the component (C) is extremely low, an
effect by the component (C) may not be sufficiently obtained, and
when the content is extremely high, the effect of friction
reduction by the component (A) may be decreased. Therefore, the
content of the component (C) in the lubricating composition of the
present invention is preferably 0.1% to 10% by mass, more
preferably 0.5% to 8% by mass and still more preferably 1% to 5% by
mass relative to the whole amount of the lubricating
composition.
[0034] [Ashless Dispersant]
[0035] Examples of the ashless dispersant include succinimide
dispersants obtained by condensation reaction of alkenyl succinic
anhydrides and polyamine compounds, succinate ester dispersants
obtained by condensation reaction of alkenyl succinic anhydrides
and polyol compounds, succinate ester amide dispersants obtained by
condensation reaction of alkenyl succinic anhydrides and
alkanolamines, Mannich base dispersants obtained by condensation of
alkylphenols and polyamines with formaldehyde, and the like. The
lubricating composition of the present invention preferably
contains, as a component (D), a succinimide dispersant because of
an increased effect of friction reduction by the component (A).
Succinimide dispersants may be divided into mono-succinimide
dispersants having one alkenyl succinimide group in a molecule and
bis-succinimide dispersants having two alkenyl succinimide groups,
and bis-succinimide dispersants are preferred because of excellent
effect of lubricity improvement. Ashless dispersants include boric
acid-modified ashless dispersants (compounds obtained by
dehydration condensation of boric acid with ashless dispersants),
and succinimide dispersants containing 0.1% to 5% by mass of boric
acid as boron atoms are particularly preferred because of an
increased effect of friction reduction by the component (A).
[0036] When the content of the component (D) in the lubricating
composition of the present invention is extremely low, an effect by
the component (D) may not be sufficiently obtained, and when the
content is extremely high, an effect corresponding to the added
amount may not be obtained and flowability may decrease. Therefore,
the content of the component (D) is preferably 0.5% to 10% by mass,
more preferably 1% to 8% by mass and still more preferably 2% to 6%
by mass relative to the whole amount of the lubricating
composition.
[0037] [Antioxidant]
[0038] Examples of the antioxidant include aromatic amine
antioxidants, phenolic antioxidants, phosphite ester antioxidants,
thioether antioxidants and the like. The lubricating composition of
the present invention preferably contains, as a component (E), a
phenolic antioxidant because the phenolic antioxidant has a high
antioxidant effect and an effect of lubricity improvement by the
component (A) may continue over a long period.
[0039] Examples of the phenolic antioxidant includes phenolic
antioxidants without ester group such as 2,6-di-t-butylphenol
2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methylphenol,
2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol,
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-methyl-6-t-butylphenol),
2,2'-methylenebis(4-ethyl-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-cyclohexylphenol),
2,2'-methylenebis(4-methyl-6-nonylphenol),
2,2'-isobutylidenebis(4,6-dimethylphenol),
2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol,
3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole,
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4'-thiobis(2-methyl-6-t-butylphenol),
2,2'-thiobis(4-methyl-6-t-butylphenol),
2,6-di-t-butyl-.alpha.-dimethylamino-p-cresol,
2,6-di-t-butyl-4-(N,N'-dimethylaminomethylphenol),
bis(3,5-di-t-butyl-4-hydroxybenzyl)sulphide,
tris{(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl}isocya
nurate, tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate,
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
bis{2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl}sul
phide,
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
tetraphthaloyl-di(2,6-dimethyl-4-t-butyl-3-hydroxybenzylsulphi de),
6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis(octylthio)-1,3,5-t
riazine,
N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide),
3,5-di-t-butyl-4-hydroxy-benzyl-phosphate diester,
bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulphide,
3,9-bis[1,1-dimethyl-2-{.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)p
ropionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane and
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benz ene;
and
[0040] phenolic antioxidants with ester group such as alkyl
3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, alkyl
3-(4-hydroxy-3-methyl-5-di-t-butylphenyl)propionate,
tetrakis{3-(4-hydroxy-3,5-di-t-butylphenyl)propionyloxymethyl}
methane, 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate glycerol
monoester, ester of 3-(4-hydroxy-3,5-di-t-butylphenyl)propionic
acid and glycerol monooleyl ether,
3-(4-hydroxy-3,5-di-t-butylphenyl)propionate butylene glycol
diester, 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate thiodiglycol
diester,
2,2-thio-{diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)}propi
onate, bis{3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid}
glycol ester.
[0041] The component (E) is preferably a phenolic antioxidant with
ester group because of an effect of lubricity improvement and a
phenolic antioxidant with one ester group is more preferred because
of high solubility in base oils, alkyl
3-(4-hydroxy-3,5-di-t-butylphenyl)propionate and alkyl
3-(4-hydroxy-3-methyl-5-di-t-butylphenyl)propionate are still more
preferred and alkyl 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate is
the most preferred. The alkyl group in the alkyl moiety in alkyl
3-(4-hydroxy-3,5-di-t-butylphenyl)propionate and alkyl
3-(4-hydroxy-3-methyl-5-di-t-butylphenyl)propionate is preferably
an alkyl group having 4 to 22 carbon atoms because of high
solubility in base oils, an alkyl group having 6 to 18 carbon atoms
is more preferred, an alkyl group having 7 to 12 carbon atoms is
still more preferred, an alkyl group having 7 to 9 carbon atoms is
yet more preferred and a branched alkyl group having 7 to 9 carbon
atoms is the most preferred.
[0042] When the content of the component (E) in the lubricating
composition of the present invention is extremely low, an
antioxidant effect is low, and when the content is extremely high,
the performance improvement commensurate with the added amount may
not be obtained and decomposition of the component (A) may be
promoted. Therefore, the content of the component (E) is preferably
0.01% to 1% by mass, more preferably 0.15% to 0.95% by mass and the
most preferably 0.2% to 0.9% by mass relative to the whole amount
of the lubricating composition. Lubricating oils for internal
combustion may contain, as an antioxidant, an amine antioxidant in
some cases. However, the lubricating composition of the present
invention preferably does not contain an amine antioxidant because
the amine antioxidant may reduce the effect of friction reduction
of the component (A) by the component (B), and even if contained,
the content thereof is preferably 0.3% by mass or less, more
preferably 0.1% by mass or less and still more preferably 0.05% by
mass or less relative to the whole amount of the lubricating
composition.
[0043] [Anti-Wear Agent]
[0044] Examples of the anti-wear agent include zinc
dithiophosphates, alkyl phosphate esters, aryl phosphate esters,
alkyl thiophosphate esters and the like. The lubricating
composition of the present invention preferably contains, as a
component (F), a zinc dithiophosphate represented by the following
general formula (3) because of a high anti-wear effect and also an
effect of lubricity improvement of the component (A):
##STR00003##
[0045] wherein R.sup.7 to R.sup.10 respectively represent an alkyl
group having 3 to 14 carbon atoms.
[0046] In the general formula (3), R.sup.7 to R.sup.10 respectively
represent an alkyl group having 3 to 14 carbon atoms. Examples of
the alkyl group having 3 to 14 carbon atoms include linear primary
alkyl groups such as a propyl group, a butyl group, a pentyl group,
a hexyl group, a heptyl group, an octyl group, a nonyl group, a
decyl group, a dodecyl group, a tridecyl group and a tetradecyl
group; branched primary alkyl groups such as an isobutyl group, an
isopentyl group, an isohexyl group, an isoheptyl group, an isooctyl
group, an isononyl group, an isodecyl group, an isododecyl group,
an isotridecyl group, an isotetradecyl group, a 2-methylpentyl
group, a 2-ethylhexyl group, a 2-propylheptyl group, a 2-butyloctyl
group, a 2-pentylnonyl group and a 3, 7-dimethyloctyl group;
secondary alkyl groups such as an isopropyl group, a secondary
butyl group, a secondary pentyl group, a secondary hexyl group, a
secondary heptyl group, a secondary octyl group, a secondary nonyl
group, a secondary decyl group, a secondary dodecyl group, a
secondary tridecyl group, a secondary tetradecyl group and a
1,3-dimethylbutyl group; tertiary alkyl groups such as a t-butyl
group and a t-pentyl group. R.sup.7 to R.sup.11 are respectively
preferably a secondary alkyl group having 4 to 14 carbon atoms,
more preferably a secondary alkyl group having 4 to 10 carbon atoms
and still more preferably a secondary alkyl group having 4 to 8
carbon atoms because of lubricity improvement of the component (A).
Specifically, a 1-methylpropyl group and a 1,3-dimethylpropyl group
are preferred. R.sup.7 to R.sup.10 may be the same group or a
combination of different groups.
[0047] When the content of the component (F) is extremely low, an
effect of improvement of an antioxidation effect may not be
sufficient, and when the content is extremely high, the performance
improvement commensurate with the added amount may not be obtained
and sludge may be generated. The content of the component (F) in
terms of the phosphorus amount derived from the component (F) is
preferably 0.001% to 3% by mass, more preferably 0.005% to 2% by
mass and the most preferably 0.01% to 1% by mass relative to the
whole amount of the lubricating composition.
[0048] The lubricating composition of the present invention
preferably contains, as a component (G), an ashless friction
regulator selected from the group consisting of polyhydric alcohol
fatty acid partial esters, (poly)glycerol alkyl ethers, alkyl
alkanolamines, alkenyl alkanolamines and fatty acid alkanolamides
because friction may be further decreased.
[0049] Examples of the polyhydric alcohol fatty acid partial ester
include glycerol monolaurate, glycerol dilaurate, glycerol
monomyristate, glycerol dimyristate, glycerol monopalmitate,
glycerol dipalmitate, glycerol monostearate, glycerol distearate,
glycerol monooleate, glycerol dioleate, diglycerol monooleate,
diglycerol dioleate, trimethylolpropane monooleate,
trimethylolpropane dioleate and the like.
[0050] Examples of the (poly)glycerol alkyl ether include glyceryl
lauryl ether, glyceryl myristyl ether, glyceryl palmityl ether,
glyceryl stearyl ether, glyceryl oleyl ether, diglyceryl oleyl
ether, triglyceryl oleyl ether and the like.
[0051] Examples of the alkyl alkanolamine include lauryl
diethanolamine, myristyl diethanolamine, palmityl diethanolamine,
stearyl diethanolamine, lauryl dipropanolamine, myristyl
dipropanolamine, palmityl dipropanolamine, stearyl dipropanolamine
and the like. Examples of the alkenyl alkanolamine include oleyl
diethanolamine, oleyl dipropanolamine and the like.
[0052] Examples of the fatty acid alkanolamide include fatty acid
monoethanolamides such as lauric acid monoethanolamide, myristic
acid monoethanolamide, palmitic acid monoethanolamide, stearic acid
monoethanolamide and oleic acid monoethanolamide; fatty acid
diethanolamides such as lauric acid diethanolamide, myristic acid
diethanolamide, palmitic acid diethanolamide, stearic acid
diethanolamide and oleic acid diethanolamide; fatty acid
N-methylethanolamides such as lauric acid N-methylethanolamide,
myristic acid N-methylethanolamide, palmitic acid
N-methylethanolamide, stearic acid N-methylethanolamide and oleic
acid N-methylethanolamide.
[0053] The component (G) is preferably a polyhydric alcohol fatty
acid partial ester and a (poly)glycerol alkyl ether, more
preferably a polyhydric alcohol fatty acid partial ester, still
more preferably a glycerol mono-fatty acid ester and the most
preferably glycerol monooleate.
[0054] When the content of the component (G) is extremely low,
sufficient effect is not obtained, and when the content is
extremely high, a performance improvement commensurate with the
added amount may not be obtained. The content of the component (G)
is preferably 0.01% to 5% by mass, more preferably 0.05% to 2% by
mass and still more preferably 0.1% to 1% by mass relative to the
whole amount of the lubricating composition.
[0055] The lubricating composition of the present invention may
further contain other lubricant additives that are generally used
for lubricating oil. Examples of the lubricant additives include
(H1) a phosphorus-based anti-wear agent or phosphorus-based
antioxidant, (H2) a sulphur-based extreme pressure agent, (H3) a
sulphur-based antioxidant, (H4) a thiophosphate-based extreme
pressure agent, (H5) a rust preventing agent, (H6) a viscosity
index improver, (H7) a metal deactivator, (H8) a defoaming agent,
(H9) a solid lubricant and the like.
[0056] Examples of (H1) the phosphorus-based anti-wear agent or
phosphorus-based antioxidant include organic phosphines, organic
phosphine oxides, organic phosphinites, organic phosphonites,
organic phosphinates, organic phosphites, organic phosphonates,
organic phosphates, organic phosphoroamidates and the like.
[0057] Examples of (H2) the sulphur-based extreme pressure agent
include sulphurized oil, sulphurized mineral oil, organic mono- or
poly-sulphides, sulphurized polyolefins, 1,3,4-thiadiazole
derivatives, thiuram disulphides, dithiocarbamate esters and the
like.
[0058] Examples of (H3) the sulphur-based antioxidant include
thiodipropionate esters, thiobis(phenol) compounds, polyhydric
alcohol esters of alkylthiopropionic acids,
2-mercaptobenzimidazole, dilauryl sulphide, amyl thioglycolate and
the like.
[0059] Examples of (H4) the thiophosphate-based extreme pressure
agent include organic trithiophosphites, organic thiophosphates and
the like.
[0060] The amounts of the components (H1) to (H4) added are
preferably about 0.01% to 2% by mass, respectively, relative to the
lubricating composition of the present invention. When the
lubricating composition of the present invention is used as an
engine oil, it is preferable to use the components in such a range
that the total phosphorus content in the lubricating composition
does not exceed 1000 ppm by mass and the total sulphur content does
not exceed 5000 ppm by mass because exhaust gas purification
catalysts may be toxified.
[0061] Examples of (H5) the rust preventing agent include oxidised
paraffin wax calcium salts, oxidised paraffin wax magnesium salts,
alkali metal salts, alkaline earth metal salts and amine salts of
tallow fatty acids, alkenyl succinic esters and alkenyl succinic
half-esters (molecular weight of the alkenyl group is about 100 to
300), sorbitan monoesters, pentaerythritol monoesters, glycerol
monoesters, nonylphenol ethoxylates, lanolin fatty acid esters,
lanolin fatty acid calcium salts and the like. The amount of the
component (H5) added is preferably about 0.1% to 15% by mass
relative to the whole amount of the lubricating composition, which
range allows sufficient exhibition of a rust preventing effect.
[0062] Examples of the component (H6), viscosity index improver,
include poly(C1-18)alkyl methacrylates, (C1-18)alkyl
acrylate/(C1-18)alkylmethacrylate copolymers, diethylaminoethyl
methacrylate/(C1-18)alkyl methacrylate copolymers,
ethylene/(C1-18)alkylmethacrylate copolymers, polyisobutylenes,
polyalkylstyrenes, ethylene/propylene copolymers, styrene/maleic
ester copolymers, styrene/maleamide copolymers, hydrogenated
styrene/butadiene copolymers, hydrogenated styrene/isoprene
copolymers and the like. The average molecular weight is about
10,000 to 1,500,000. The amount of the component (H6) added is
preferably about 0.1% to 20% by mass relative to the whole amount
of the lubricating composition.
[0063] Examples of the component (H7), metal deactivator, include
N,N'-salicylidene-1,2-propanediamine, alizarin, tetraalkyl thiuram
disulphides, benzotriazole, benzimidazole, 2-alkyl
dithiobenzimidazoles, 2-alkyl dithiobenzothiazoles,
2-(N,N-dialkylthiocarbamoyl)benzothiazoles,
2,5-bis(alkyldithio)-1,3,4-thiadiazoles,
2,5-bis(N,N-dialkylthiocarbamoyl)-1,3,4-thiadiazoles and the like.
The amount of the component (H7) added is preferably about 0.01% to
5% by mass relative to the lubricating composition.
[0064] Examples of the component (H8), defoaming agent, include
polydimethylsilicone, trifluoropropylmethylsilicone, colloidal
silica, polyalkyl acrylates, polyalkyl methacrylates, alcohol
ethoxylates/propoxylates, fatty acid ethoxylates/propoxylates,
sorbitan partial fatty acid esters and the like. The amount of the
component (H8) added is preferably about 1 to 1000 ppm by mass
relative to the whole amount of the lubricating composition.
[0065] Examples of the component (H9), solid lubricant, include
graphite, molybdenum disulphide, polytetrafluoroethylene, fatty
acid alkaline earth metal salts, mica, cadmium dichloride, cadmium
diiodide, calcium fluoride, lead iodide, lead oxide, titanium
carbide, titanium nitride, aluminium silicate, antimony oxide,
cerium fluoride, polyethylene, diamond powder, silicon nitride,
boron nitride, carbon fluoride, melamine isocyanurate and the like.
The amount of the component (H9) added is preferably about 0.005%
to 2% by mass relative to the whole amount of the lubricating
composition.
[0066] Each of the components (H1) to (H9) added may appropriately
be one or more compounds.
[0067] The lubricating composition of the present invention may be
used for lubrication of various applications. For example, engine
oils such as gasoline engine oil and diesel engine oil, industrial
lubricating oil, turbine oil, machine oil, bearing oil, compressor
oil, hydraulic oil, operating oil, internal combustion oil,
refrigerant oil, gear oil, automatic transmission fluid (ATF),
continuously variable transmission fluid (CVTF), transaxle fluid,
metal processing oil and the like may be mentioned. Alternatively,
the lubricating composition may be added and used in various
greases for slide bearings, roller bearings, gear wheels, universal
joints, torque limiters, automobile constant velocity joints
(CVJs), ball joints, wheel bearings, constant velocity gears,
transmission gears and the like.
EXAMPLES
[0068] The present invention is hereinafter more specifically
described by way of the Examples. In the Examples, "%" is based on
the mass unless otherwise stated.
[0069] With the following compounds and base oils, lubricating
compositions of Examples 1 to 10 and Comparative Examples 1 to 5
having the compositions indicated in Table 1 were prepared. The
values of the compositions indicated in the table are in parts by
mass of compounds when the whole amount of the lubricating
composition is regarded as 100 parts by mass.
[0070] (A1) Compound of general formula (1), wherein R.sup.1 and
R.sup.2 are respectively a 2-ethylhexyl group, R.sup.3 and R.sup.4
are respectively a branched tridecyl group, X.sup.1 and X.sup.2 are
respectively a sulphur atom and X.sup.3 and X.sup.4 are
respectively an oxygen atom (Mo content: 18.1%) [0071] (A2)
Compound of general formula (1), wherein R.sup.4 to R.sup.4 are
respectively a 2-ethylhexyl group, X.sup.4 and X.sup.2 are
respectively a sulphur atom and X.sup.3 and X.sup.4 are
respectively an oxygen atom (Mo content: 20.7%) [0072] (B1)
Compound of general formula (2), wherein R.sup.5 and R.sup.6 are
respectively a 2-ethylhexyl group [0073] (B2) Compound of general
formula (2), wherein R.sup.5 and R.sup.6 are respectively a
branched tridecyl group [0074] (C1) Calcium salicylate (Ca content:
10%, TBN: 280 mgKOH/g) [0075] (C2) Boron-modified calcium
salicylate (Ca content: 10%, boron content: 0.5%, TBN: 275 mgKOH/g)
[0076] (C3) Magnesium salicylate (Mg content: 6.0%, TBN: 280
mgKOH/g) [0077] (C'1) Calcium sulphonate (Ca content: 11.4%, TBN:
300 mgKOH/g) [0078] (D1) Bis(polyalkenyl succinimide) [0079] (D2)
Borated alkenyl succinimide (boron content: 0.34%) [0080] (D'1)
Mannich base dispersant [0081] (E1) Phenolic antioxidant with ester
group indicated below:
##STR00004##
[0082] wherein R.sup.11 is a branched alkyl group having 7 to 9
carbon atoms
[0083] (F1) Compound of general formula (3), wherein R.sup.7 to
R.sup.10 are respectively a 1-methylpropyl group or a
1,3-dimethylbutyl group [0084] (Base oil) Mineral oil-based oil
with high VI having a kinetic viscosity at 40.degree. C. of 18.3
mm.sup.2/s and a viscosity index of 126
[0085] The lubricating compositions of Examples 1 to 10 and
Comparative Examples 1 to 5 were measured for coefficient of
friction and corrosiveness to copper plates according to the
methods indicated below. The results are indicated in Table 1.
[0086] [Method for Determining Coefficient of Friction] [0087]
Tester used: SRV tester (produced by Optimol Instruments [0088]
Pruftechnik GmbH, model: type 3) Evaluation conditions: [0089] The
coefficient of friction is measured under line contact conditions
of a cylinder on a plate. [0090] Load: 200 N [0091] Temperature:
80.degree. C. [0092] Measurement time: 15 minutes [0093] Stroke: 1
mm [0094] Upper cylinder: .PHI.15.times.22 mm (material: SUJ-2)
[0095] Lower plate: .PHI.24.times.6.85 mm (material: SUJ-2) [0096]
Evaluation method: The average coefficient of friction between 5 to
15 minutes is regarded as the coefficient of friction obtained by
the present test. A lower coefficient of friction indicates better
lubricity.
[0097] [Test Method of Corrosiveness to Copper Plates] [0098] Test
method: according to JIS K2513 (Petroleum products-Corrosiveness to
copper-Copper strip test) [0099] Test temperature: 100.degree. C.
[0100] Test period: 3 hours [0101] Evaluation method: The extent of
corrosion is judged by comparing the discoloration of copper plates
with the corrosion standard of the copper plate according to JIS
K2513. The smaller number means less corrosion, and for the same
numbers, corrosion is from low to high in the order of
a.fwdarw.b.fwdarw.c. Systematic corrosion according to the
corrosion standard of the copper plate is indicated in Table 1.
TABLE-US-00001 [0101] Examples 1 2 3 4 5 6 7 8 A1 0.39 0.39 0.39
0.39 0.39 -- 0.39 0.39 A2 -- -- -- -- -- 0.34 -- -- B1 0.005 0.010
0.013 0.005 -- 0.010 -- 0.005 B2 -- -- -- 0.005 0.010 -- 0.010
0.005 C1 2.8 2.8 2.8 2.8 2.8 2.8 -- -- C2 -- -- -- -- -- -- 2.8 --
C'1 -- -- -- -- -- -- -- 2.8 D1 4 4 4 4 4 4 4 4 D2 -- -- -- -- --
-- -- -- D'1 -- -- -- -- -- -- -- -- E1 0.8 0.8 0.8 0.8 0.8 0.8 0.8
0.8 F1 1 1 1 1 1 1 1 1 Base oil Balance Balance Balance Balance
Balance Balance Balance Balance Mo content ppm 700 700 700 700 700
700 700 700 100 * (amine/Mo) 7.1 14.2 18.6 14.2 14.2 14.2 14.2 14.2
Friction coefficient 0.063 0.062 0.061 0.062 0.061 0.062 0.062
0.060 Copper plate corrosiveness 1a 1a 1b 1a 1a 1a 1a 1a Examples
Comparative Examples 9 10 1 2 3 4 5 A1 0.39 0.39 0.39 0.39 -- -- --
A2 -- -- -- -- 0.34 0.34 -- B1 0.010 0.005 -- 0.012 -- -- 0.010 B2
-- 0.005 -- 0.012 -- 0.025 -- C1 2.8 2.8 2.8 2.8 2.8 2.8 2.8 C2 --
-- -- -- -- -- -- C'1 -- -- -- -- -- -- -- D1 -- -- 4 4 4 4 4 D2 4
-- -- -- -- -- -- D'1 -- 4 -- -- -- -- -- E1 0.8 0.8 0.8 0.8 0.8
0.8 0.8 F1 1 1 1 1 1 1 1 Base oil Balance Balance Balance Balance
Balance Balance Balance Mo content ppm 700 700 700 700 700 700 0
100 * (amine/Mo) 14.2 14.2 -- 34.2 -- 35.5 -- Friction coefficient
0.062 0.064 0.068 0.060 0.067 0.061 0.121 Copper plate
corrosiveness 1a 1a 1a 2d 1a 2d 1a
* * * * *