[0001] The present invention provides lubricating oil compositions, and in particular lubricating
oil compositions used as machine oils, hydraulic oils, turbine oils, compressor oils,
gear oils, sliding friction oils, bearing oils and calibration oils.
[0002] Corrosion resistance is required as a fundamental property of lubricating oils in
machine installations so as to maintain performance. The lubricating oil temperature
within tanks in machines and apparatus rises and falls in accordance with conditions
of use, and therefore the lubricating oil within the tanks may be subject to admixture
with condensed water or admixture with moisture because of leaks from cooling water
pipes.
[0003] US2006/090393 relates to the use of epoxidized esters as lubricant additives for imparting anticorrosion,
anti-fatigue and anti-wear properties to the lubricant.
[0004] US-A-5275749 relates to lubricating oil compositions comprising N-acyl-N-hydrocarbonoxyalkyl aspartic
acid esters which exhibit corrosion inhibition, anti-wear properties and improved
demulsibility.
WO 2008/031808 published on 20.03.2008 claiming the priority of 11.09.2006 discloses lubricating
oil compositions comprising an aspartic acid derivative, an epoxidised fatty acid
ester and a fatty acid ester of a polyhydric alcohol.
[0005] It is also necessary to inhibit as far as practicable the generation of sludge in
the lubricating oils used in machine installations. If large quantities of sludge
are generated because of deterioration under heat, for example, blockage of oil filter
meshes may occur and sufficient supply of lubricating oil may not be possible, giving
rise to breakdowns. Also, the sludge generated may accumulate in bearing parts and
an adequate oil film may not form because of lacquer generated on bearing parts, giving
rise to bearing damage. Further, in hydraulic installations, sludge may block the
parts of the hydraulic circuit known as servo pumps, giving rise to breakdowns of
the installation. Lubricating oil compositions with low sludge generation are therefore
required.
[0006] Furthermore, in recent years good friction properties have been required of industrial
lubricating oil compositions. This is because of the requirements of efficiently reducing
friction losses in machines and apparatus and achieving large energy economies through
having a low friction coefficient (µ). Also, hydraulic apparatus is widely used in
construction machines and so on, and if the friction coefficient of the lubricating
oils used for the hydraulic oil actuating the machinery is high, the phenomenon of
minute stick-slip may occur in the sliding friction parts of the reciprocating packing
of the hydraulic cylinders, and chatter, vibration, squealing and other abnormal sounds
may occur in the cylinders, so that it becomes impossible to control the hydraulic
plant with satisfactory precision. See Japanese Laid-open Patent
9-111277 (1997). In consequence it is necessary to reduce the friction coefficient of the lubricating
oil so that the hydraulic cylinders move smoothly and accurately.
[0007] The present invention aims to obtain a lubricating oil composition having superior
corrosion resistance properties as well as producing only small amounts of sludge.
However, anti-corrosives added with a view to improving corrosion resistance may be
substances giving rise to sludge, as a result of deterioration under heat. An important
problem therefore is strike a balance between maintaining the anti-corrosive effect
while inhibiting sludge.
[0008] Further important problems are to reduce the friction coefficients of lubricating
oils and to obtain industrial lubricating oils having high energy savings. If a lubricating
oil composition which resolves these problems is used for the hydraulic oils in hydraulic
apparatus, the phenomena of chatter, vibration, squealing and other abnormal noises
will not occur in the hydraulic cylinders and it will become possible to control the
hydraulic apparatus with satisfactory precision. The present invention aims to obtain
a lubricating oil composition which inhibits the generation of corrosion and sludge,
which has abundant energy saving properties and which has good operational efficiency.
[0009] To this end the present invention provides a lubricating oil composition suitable
as an industrial lubricating oil such as hydraulic oil by adding an aspartic acid
derivative and an epoxidised ester compound as additives to a base oil, preferably
being a highly refined base oil or a synthetic oil, having a sulphur content of not
more than 300 ppm. Also, in a preferred embodiment, the present invention provides
a lubricating oil composition with even less sludge generation and superior energy
saving properties by further adding as an additive an aliphatic amine.
[0010] According to the present invention, it is possible to obtain a lubricating oil composition
which inhibits the generation of corrosion and sludge. Further, it is possible to
reduce effectively the friction losses caused in various kinds of industrial apparatus,
and to ensure savings on energy. Also, if it is used as a hydraulic oil, it is possible,
by reducing the friction coefficient, to control the hydraulic apparatus with satisfactory
precision and without the occurrence of phenomena such as chatter, vibration, squealing
or other abnormal noises in the hydraulic cylinders.
[0011] For the base oils of this lubricating oil composition it is possible to use the mineral
oils and synthetic oils known as highly refined base oils. In particular it is possible
to use, singly or as mixtures, base oils which belong to Group I, Group II, Group
III, Group IV and so on of the API (American Petroleum Institute) base oil categories.
For the base oils used here, the elemental sulphur content should be not more than
300 ppm, preferably not more than 200 ppm, more preferably not more than 100 ppm and
most preferably not more than 50 ppm. Also, it is preferred that the density is from
0.8 to 0.9, preferably from 0.8 to 0.865, and more preferably from 0.81 to 0.83. The
aromatic content is preferably less than 3%, more preferably less than 2% and even
more preferably less than 0.1.
[0012] Group II base oils include, for example, paraffinic mineral oils obtained by appropriate
use of a suitable combination of refining processes such as hydrorefining and dewaxing
in respect of lubricating oil fractions obtained by atmospheric distillation of crude
oil. Group II base oils refined by hydrorefining methods such as the Gulf Company
method have a total sulphur content of less than 10 ppm and an aromatic content of
not more than 5% and so are suitable for the present invention. The viscosity of these
base oils is not specially limited, but the viscosity index may be from 80 to 120
and preferably from 100 to 120. The kinetic viscosity at 40°C (ASTM D445) is preferably
from 2 to 680 mm
2/s and even more preferably from 8 to 220 mm
2/s. Also, the total sulphur content may be less than 300 ppm, preferably less than
200 ppm and even more preferably less than 10 ppm. The total nitrogen content to be
less than 10 ppm and preferably less than 1 ppm. In addition, oils with an aniline
point of from 80 to 150°C and preferably from 100 to 135°C may be used.
[0013] Among Group III base oils and Group II+ base oils, paraffinic mineral oils manufactured
by a high degree of hydrorefining in respect of lubricating oil fractions obtained
by atmospheric distillation of crude oil, base oils refined by the Isodewax process
which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins,
and base oils refined by the Mobil wax isomerisation process are suitable, for example.
The viscosity of these base oils is not specially limited, but the viscosity index
may be from 95 to 145 and preferably from 100 to 140. The kinetic viscosity at 40°C
may preferably be from 2 to 680 mm
2/s and even more preferably from 8 to 220 mm
2/s. Also, the total sulphur content to be from 0 to 100 ppm and preferably less than
10 ppm. The total nitrogen content should be less than 10 ppm and preferably less
than 1 ppm. In addition, oils with an aniline point of from 80 to 150°C and preferably
from 110 to 135°C may be used.
[0014] GTLs (gas to liquid derived base oils) synthesised by the Fischer-Tropsch method
of converting natural gas to liquid fuel have a very low sulphur content and aromatic
content compared with mineral oil base oils refined from crude oil and have a very
high paraffin constituent ratio, and so have excellent oxidative stability, and because
they also have extremely small evaporation losses, they are suitable as base oils
for the present invention. The viscosity characteristics of GTL base oils are not
specially limited, but normally the viscosity index should be from 130 to 180 and
preferably from 140 to 175. Also, the kinetic viscosity at 40°C may be from 2 to 680
mm
2/s and even more preferably from 5 to 120 mm
2/s. Normally, the total sulphur content may also be less than 10 ppm and the total
nitrogen content may be less than 1 ppm. A commercial example of such a GTL derived
base oil is Shell XHVI (registered trademark).
[0015] As examples of synthetic oils mention may be made of polyolefins, alkylbenzenes,
alkylnaphthalenes, esters, polyoxyalkylene glycols, polyphenyl ethers, dialkyldiphenyl
ethers, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins)
and silicone oils.
[0016] The above-mentioned polyolefins include polymers of various olefins or hydrides thereof.
Any olefin may be used, and as examples mention may be made of ethylene, propylene,
butene and α-olefins with five or more carbons. In the manufacture of polyolefins,
one kind of the above-mentioned olefins may be used singly or two or more kinds may
be used in combination. Particularly suitable are the polyolefins called poly-α-olefins
(PAO). These are base oils of Group IV.
[0017] The viscosity of these synthetic oils is not specially limited, but the kinetic viscosity
at 40°C may preferably be from 2 to 680 mm
2/s and even more preferably from 8 to 220 mm
2/s.
[0018] The amount of the aforementioned base oil in the lubricating oil composition of the
present invention is not specially limited, but on the basis of the total amount of
the lubricating oil composition it is usually not less than 60 % by weight, preferably
not less than 80 % by weight, more preferably not less than 90 % by weight and yet
more preferably not less than 95 % by weight.
[0019] The aspartic acid derivatives are shown by the general formula 1.

[0020] In the aforementioned general formula 1, X
1 and X
2 are each hydrogen atoms or same or different alkyl groups or hydroxyalkyl groups
having from 3 to 6 carbon atoms, and for preference a 2-methylpropyl group and a tertiarybutyl
group respectively are good. X
3 refers to alkyl groups constituted of from 1 to 30 carbon atoms, or alkyl groups
having ether bonds, or hydroxyalkyl groups. For example, octadecyl groups, alkoxypropyl
groups and 3-(C
6-C
18) hydrocarbon oxy (C
3-C
6) alkyl groups are good, and preferably cyclohexyloxypropyl groups, 3-octyloxypropyl
groups, 3-isooctyloxypropyl groups, 3-decyloxypropyl groups, 3-isodecyloxypropyl groups
and 3-(C
12-C
16) alkoxypropyl groups. X
4 refers to saturated or unsaturated carboxylic groups having from 1 to 30 carbon atoms,
or alkyl groups having from 1 to 30 carbons, or alkenyl groups, or hydroxyalkyl groups.
For example, propionic acid groups and propionyl acid groups are good.
[0021] The aforementioned aspartic acid derivative preferably has an acid number as determined
by JIS K2501 of from 10 to 200 mgKOH/g, and preferably of from 50 to 150 mgKOH/g.
The aspartic acid derivative is used in the lubricating agent composition in the order
of from 0.01 to 5 % by weight and preferably in the order of from 0.05 to 2 % by weight.
[0022] The epoxidised ester compound may be manufactured by epoxidating esters of rapeseed
oil, soybean oil, linseed oil, castor oil, coconut oil, palm oil, palm kernel oil,
sunflower oil, rice-bran oil, safflower oil, beef tallow, pork tallow and so on. Mention
may be made of epoxidised rapeseed oil esters, epoxidised soybean oil esters, epoxidised
linseed oil esters, epoxidised castor oil esters, epoxidised safflower oil esters,
and also of those manufactured by epoxidating oleic acid esters such as methyl epoxystearate,
butyl epoxystearate and octyl epoxystearate.
[0023] Also, the alcohol residues of the esters may be alkyl groups, or alkyl groups having
ether bonds, or hydroxyalkyl groups, and preferably butyl groups, isobutyl groups
or 2-ethylhexyl groups.
[0024] As examples, mention may be made of epoxidised rapeseed fatty acid isobutyl ester,
epoxidised rapeseed fatty acid 2-ethylhexyl ester and epoxidised linseed oil fatty
acid butyl ester. The main constituents of ordinary rapeseed fatty acids are fatty
acids of 18 carbons with oleic acid 63%, linolic acid 20% and linolenic acid 8%. The
main constituents of linseed fatty acids are fatty acids of 18 carbons with oleic
acid 21%, linolic acid 13% and linolenic acid 57%.
[0025] These epoxidised ester compounds are known as plasticisers and stabilisers in rubbers
and plastics. The amount of epoxidised ester compound blended in the lubricating oil
composition is from 0.01 to 5 per cent by weight, preferably from 0.01 to 2 per cent
by weight, and even more preferably from 0.01 to 1 per cent by weight.
[0026] An aliphatic amine compound may further be incorporated in this lubricating oil composition,
and as examples of such aliphatic amine compounds mention may be made of the primary
amines shown in General Formula (2) and General Formula (3) and of the secondary amines
show in General Formula (4).
Formula 2 H
2N - X
5 (2)
[0027] In the aforementioned formula (2), X
5 refers to saturated or unsaturated alkyl groups having from 1 to 30 carbon atoms.
For example, mention may be made of laurylamine, coconut amine, n-tridecylamine, myristylamine,
n-pentadecylamine, n-palmitylamine, n-heptadecylamine, n-stearylamine, isostearylamine,
n-nonadecylamine, n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine,
n-pentacosylamine, oleylamine, beef tallow amine, hydrogenated beef tallow amine and
soybean amine. Preferably the number of carbons of X
5 is from 8 to 24 and more preferably from 12 to 18. Also, X
5 may be a tertiary alkyl group in either a straight-chain aliphatic or a branched-chain
aliphatic.
Formula 3 H
2N - X
6 - NH
2 (3)
[0028] In the aforementioned formula (3), X
6 refers to saturated or unsaturated alkylene groups having from 1 to 30 carbon atoms.
For example, mention may be made of ethylenediamines such as laurylethylenediamine,
coconut ethylenediamine, n-tridecylethylenediamine, myristylethylenediamine, n-pentadecylethylenediamine,
n-palmitylethylenediamine, n-heptadecylethylenediamine, n-stearylethylenediamine,
isostearylethylenediamine, n-nonadecylethylenediamine, n-eicosylethylenediamine, n-heneicosylethylenediamine,
n-docosylethylenediamine, n-tricosylethylenediamine, n-pentacosylethylenediamine,
oleylethylenediamine, beef tallow ethylenediamine, hydrogenated beef tallow ethylenediamine
and soybean ethylenediamine. Preferably the number of carbons of X
6 is from 8 to 24 and more preferably from 12 to 18.
Formula 4 X
7 - NH - X
8 (4)
[0029] In the aforementioned formula (4), X
7 and X
8 refer to saturated or unsaturated alkyl groups having from 1 to 30 carbon atoms.
For example, mention may be made of dilaurylamine, di-coconut amine, di-n-tridecylamine,
din-myristylamine, di-n-pentadecylamine, di-n-palmitylamine, di-n-heptadecylamine,
di-n-stearylamine, diisostearylamine, di-n-nonadecylamine, di-n-eicosylamine, di-n-heneicosylamine,
di-n-docosylamine, di-n-tricosylamine, di-n-pentacosylamine, dioleylamine, di-beef
tallow amine, di-hydrogenated beef tallow amine and di-soybean amine. Preferably the
number of carbons of X
7 and X
8 is from 8 to 24 and more preferably from 12 to 18. X
7 and X
8 may be the same or different.
[0030] At least one kind of these aliphatic amines selected from the aforementioned groups
may be used in the lubricating agent composition in the order of approximately 0.005
to 5 % by weight, and preferably in the order of approximately 0.01 to 1 % by weight.
[0031] Apart from the aforementioned constituents, it is possible to make suitable use of
various additives as necessary in order further to improve performance. As examples
of these, mention may be made of anti-oxidants, metal deactivators, extreme pressure
agents, oiliness improvers, defoaming agents, viscosity index improvers, pour point
depressants, detergent-dispersants, anticorrosion agents, demulsifiers, and other
lubricating agents known in the art.
[0032] The anti-oxidants used in the present invention are preferably those used in practice
in lubricating oils, and mention may be made of phenol-based anti-oxidants, amine-based
anti-oxidants and sulphur-based anti-oxidants. These anti-oxidants may be used singly
or in combinations within the range of 0.01 to 5 parts by weight relative to 100 parts
by weight of the base oil.
[0033] As examples of the above mentioned amine-based anti-oxidants, mention may be made
of dialkyl-diphenylamines such as p,p'-dioctyl-diphenylamine (Nonflex OD-3 manufactured
by Seiko Kagaku Ltd.), p,p'-di-α-methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'-octylphenylamine,
monoalkyldiphenylamines such as mono-t-butyldiphenylamine and monooctyldiphenylamine,
bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine,
alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and N-t-dodecylphenyl-1-naphthylamine,
aryl-naphthylamines such as 1-naphthylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine,
N-hexylphenyl-2-naphthylamine and N-octylphenyl-2-naphthylamine, phenylenediamines
such as N,N'-diisopropyl-p-phenylenediamine and N,N'-diphenyl-p-phenylenediamine,
and phenothiazines such as Phenothiazine (manufactured by Hodogaya Chemical Co. Ltd.)
and 3,7-dioctylphenothiazine.
[0034] As examples of sulphur-based anti-oxidants, mention may be made of dialkylsulphides
such as didodecylsuplhide and dioctadecylsulphide, thiodipropionic acid esters such
as didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate
and dodecyloctadecyl thiodipropionate, and 2-mercaptobenzimidazole.
[0035] The phenol-based anti-oxidants include 2-t-butylphenol, 2-t-butyl-4-methylphenol,
2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol,
3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (Antage DBH, manufactured by
Kawaguchi Kagaku Co. Ltd.), 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-alkylphenols such
as 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol, and 2,6-di-t-butyl-4-alkoxyphenols
such as 2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol.
[0036] They also include 3,5-di-t-butyl-4-hydroxybenzylmercapto-octyl acetate, alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionates such as n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (Yoshinox
SS, manufactured by Yoshitomi Pharmaceutical Industries Co. Ltd.), n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate, n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate and benzenepropanoic acid 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched
alkyl esters (Irganox L135, manufactured by Ciba Speciality Chemicals Co. Ltd), 2,6-di-t-butyl-α-dimethylamino-p-cresol,
and 2,2-methylenebis(4-alkyl-6-t-butylphenols) such as 2,2'-methylenebis(4-methyl-6-t-butylphenol)
(Antage W-400, manufactured by Kawaguchi Kagaku Co. Ltd.) and 2,2'-methylenebis(4-ethyl-6-t-butylphenol)
(Antage W-500, manufactured by Kawaguchi Kagaku Co. Ltd.).
[0037] They further include bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butylphenol)
(Antage W-300, manufactured by Kawaguchi Kagaku Co. Ltd.), 4,4'-methylenebis(2,6-di-t-butylphenol)
(Ionox 220AH, manufactured by Shell Japan Co. Ltd.), 4,4'-bis(2,6-di-t-butylphenol),
2,2-(di-p-hydroxyphenyl)propane (Bisphenol A, manufactured by Shell Japan Co. Ltd.),
2,2-bis(3,5-dit-butyl-4-hydroxyphenyl)propane, 4,4-cyclohexylidenebis(2,6-t-butylphenol),
hexamethylene glycolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox L109,
manufactured by Ciba Speciality Chemicals Co. Ltd), triethylene glycolbis[3-(3-t-qutyl-4-hydroxy-5-methylphenyl)
propionate] (Tominox 917, manufactured by Yoshitomi Pharmaceutical Industries Co.
Ltd.), 2,2'-thio-[diethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox
L115, manufactured by Ciba Speciality Chemicals Co. Ltd), 3,9-bis{1,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}
2,4,8,10-tetraoxaspiro[5,5]undecane (Sumilizer GA80, manufactured by Sumitomo Chemicals
Co. Ltd.), 4,4'-thiobis(3-methyl-6-t-butylphenol) (Antage RC, manufactured by Kawaguchi
Kagaku Co. Ltd.) and 2,2'-thiobis(4,6-di-t-butylresorcinol).
[0038] Mention may also be made of tetrakis[methylene-3-3(3,5-di-t-butyl-4-hydroxyphenyl)
propionate] methane (Irganox L101, manufactured by Ciba Speciality Chemicals Co. Ltd),
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane (Yoshinox 930, manufactured
by Yoshitomi Pharmaceutical Industries Co. Ltd.), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)
benzene (Ionox 330, manufactured by Shell Japan Co. Ltd.), bis-[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)
butyric acid] glycol ester, polyphenols such as 2-(3',5'-di-t-butyl-4-hydroxyphenyl)methyl-4-(2",4"-di-t-butyl-3"-hydroxyphenyl)methyl-6-t-butylphenol
and 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, and phenol-aldehyde
condensates such as condensates of p-t-butylphenol and formaldehyde and condensates
of p-t-butylphenol and acetaldehyde.
[0039] As examples of phosphorus-based anti-oxidants, mention may be made of triaryl phosphites
such as triphenyl phosphite and tricresyl phosphite, trialkyl phosphites such as trioctadecyl
phosphite and tridecyl phosphite, and tridodecyl trithiophosphite.
[0040] The metal deactivators which can be combined with the lubricating oil composition
of the present invention include benzotriazole, benzotriazole derivatives of the 4-alkyl-benzotriazoles
such as 4-methyl-benzotriazole and 4-ethyl-benzotriazole, 5-alkyl-benzotriazoles such
as 5-methyl-benzotriazole and 5-ethyl-benzotriazole, 1-alkyl-benzotriazoles such as
1-dioctylaminomethyl-2,3-benzotriazole and 1-alkyl-tolutriazoles such as 1-dioctylaminomethyl-2,3-tolutriazole,
benzimidazole, and benzimidazole derivatives of the 2-(alkyldiothio)-benzimidazoles
such as 2-(octyldithio)-benzimidazole, 2-(decyldithio)-benzimidazole and 2-(dodecyldithio)-benzimidazole
and 2-(alkyldithio)-toluimidazoles such as 2-(octyldithio)-toluimidazole, 2-(decyldithio)-toluimidazole
and 2-(dodecyldithio)- toluimidazole.
[0041] They also include indazole, indazole derivatives of the toluindazole derivatives
such as 4-alkyl-indazoles and 5-alkyl-indazoles, benzothiazole, and benzothiazole
derivatives of the 2-mercaptobenzothiazole derivatives (Thiolite B-3100, manufactured
by Chiyoda Kagaku Co. Ltd.), 2-(alkyldithio)benzothiazoles such as (hexyldithio)benzothiazole
and 2-octyldithio)benzothiazole, 2-(alkyldithio)toluthiazoles such as 2-(hexyldithio)toluthiazole
and 2-(octyldithio)toluthiazole, 2-(N,N-dialkyldithiocarbamyl)benzothiazoles such
as 2-(N,N-diethyldithiocarbamyl)-benzothiazole, 2-(N,N-dibutyldithiocarbamyl)benzothiazole
and 2-(N,N-dihexyldithiocarbarnyl)-benzothiazole, 2-(N,N-dialkyldithiocarbarnyl)-toluthiazoles
such as 2-(N,N-diethyldithiocarbamyl)toluthiazole, 2-(N,N-dibutyldithiocarbamyl)-toluthiazole
and 2-(N,N-dihexyldithiocarbamyl)toluthiazole,
[0042] They further include benzoxazole derivatives of the 2-(alkyldithio)benzoxazoles such
as 2-(octyldithio)-benzoxazole, 2-(decyldithio)benzoxazole and 2-(dodecyldithio)benzoxazole,
and 2-(alkyldithio)toluoxazoles such as 2-(octyldithio)toluoxazole, 2-(decyldithio)toluoxazole
and 2-(dodecyldithio)toluoxazole, thiadiazole derivatives of the 2,5-bis(alkyldithio)-1,3-4-thiadiazoles
such as 2,5-bis(heptyldithio)-1,3-4-thiadiazole, 2,5-bis(nonyldithio)-1,3-4-thiadiazole,
2,5-bis(dodecyldithio)-1,3-4-thiadiazole and 2,5-bis(octadecyldithio)-1,3-4-thiadiazole,
2,5-bis(N,N-dialkyldithiocarbamyl)-1,3-4-thiadiazoles such as 2,5-bis(N,N-diethyldithiocarbamyl)-1,3-4-thiadiazole,
2,5-bis(N,N-dibutyldithiocarbamyl)-1,3-4-thiadiazole and 2,5-bis(N,N-dioctyldithiocarbamyl)-1,3-4-thiadiazole,
2-N,N-dialkyldithiocarbamyl-5-mercapto-1,3,4-thiadiazoles such as 2-N,N-dibutyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole
and 2-N,N-dioctyldithiocarbamyl-5-mercapto-1,3,4-thiadiazole, and triazole derivatives
of 1-alkyl-2,4-triazoles such as 1-di-octylaminomethyl-2,4-triazole. These metal deactivators
may be used singly or in combinations within the range of 0.01 to 0.5 parts by weight
relative to 100 parts by weight of the base oil.
[0043] In order to impart wear resistance and extreme pressure properties to the lubricating
oil composition of the present invention it is possible also to add phosphorus compounds.
As examples of compounds suitable for the present invention, mention may be made of
phosphate esters, acidic phosphate esters, amine salts of acidic phosphate esters
chlorinated phosphate esters, phosphite esters, phosphorothionates, zinc dithiophosphates,
esters or derivatives thereof of dithiophosphates and alkanol or polyether-type alcohols,
phosphorus-containing carboxylic acids, and phosphorus-containing organic carboxylate
esters. These phosphorus compounds may be used singly or in combinations within the
range of 0.01 to 2 parts by weight relative to 100 parts by weight of the base oil.
[0044] As examples of the aforementioned phosphate esters, mention may be made of tributyl
phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl
phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl
phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate,
trihexadecyl phosphate, triheptadecyl phosphate, triocyadecyl phosphate, trioleyl
phosphate, triphenyl phosphate, tris(iso-propylphenyl) phosphate, triallyl phosphate,
tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate and xylenyldiphenyl
phosphate.
[0045] As specific examples of the aforementioned acidic phosphate esters, mention may be
made of monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate,
monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl
acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl
acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl
acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl
acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate,
diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid
phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate,
ditetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate,
diheptadecyl acid phosphate, dioctadecyl acid-phosphate and dioleyl acid phosphate.
[0046] As examples of the aforementioned amine salts of acidic phosphate esters, mention
may be made of salts with amines of the of the above mentioned acidic phosphate esters
such as methylamines, ethylamines, propylamines, butylamines, pentylamines, hexylamines,
heptylamines, octylamines, dimethylamines, diethylamines, dipropylamines, dibutylamines,
dipentylamines, dihexylamines, diheptylamines, dioctylamines, trimethylamines, triethylamines,
tripropylamines, tributylamines, tripentylamines, trihexylamines, triheptylamines
and trioctylamines.
[0047] As examples of the aforementioned phosphite esters, mention may be made of dibutyl
phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite,
dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl
phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite,
trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl
phosphite, triundecyl phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl
phosphite and tricresyl phosphite.
[0048] As examples of the aforementioned phosphorothionates, mention may be made specifically
of tributyl phosphorothionate, tripentyl phosphorothionate, trihexyl phosphorothionate,
triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate,
tridecyl phosphorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate,
tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate,
trihexadecyl phosphorothionate, triheptadecyl phosphorothionate, trioctadecyl phosphorothionate,
trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothionate,
trixylenyl phosphorothionate, cresyldiphenyl phosphorothionate, xylenyldiphenyl phosphorothionate,
tris(n-butylphenyl) phosphorothionate, tris(iso-butylphenyl) phosphorothionate, tris(s-butylphenyl)
phosphorothionate and tris(t-butylphenyl) phosphorothionate. These may also be used
in mixtures thereof.
[0049] As examples of the aforementioned zinc dithiophosphates, mention may be made in general
of zinc dialkyl dithiophosphates, zinc diaryl dithiophosphates and zinc arylalkyl
dithiophosphates. For example, with respect to the alkyl groups of the zinc dialkyl
dithiophosphates, zinc dialkyl dithiophosphates having primary or secondary alkyl
groups of 3 to 22 carbons or alkylaryl groups substituted with alkyl groups of 3 to
18 carbons may be used. As specific examples of zinc dialkyl dithiophosphates mention
may be made of zinc dipropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc dipentyl
dithiophosphate, zinc dihexyl dithiophosphate, zinc diisopentyl dithiophosphate, zinc
diethylhexyl dithiophosphate, zinc dioctyl dithiophosphate, zinc dinonyl dithiophosphate,
zinc didecyl dithiophosphate, zinc didodecyl dithiophosphate, zinc dipropylphenyl
dithiophosphate, zinc dipentylphenyl dithiophosphate, zinc dipropylmethylphenyl dithiophosphate,
zinc dinonylphenyl dithiophosphate, and zinc didodecylphenyl dithiophosphate.
[0050] Pour-point depressants and viscosity index improvers may also be added to the lubricating
oil composition of the present invention in order to improve low-temperature flow
characteristics and viscosity characteristics. As examples of viscosity index improvers,
mention may be made of non-dispersant viscosity index improvers as exemplified by
polymethacrylates and olefin polymers such as ethylene-propylene copolymers, styrene-diene
copolymers, polyisobutylene and polystyrene, or dispersant-type viscosity index improvers
which are copolymerised with nitrogen-containing monomers. The amount thereof added
may be within the range of 0.05 to 20 parts by weight relative to 100 parts by weight
of base oil.
[0051] As examples of pour-point depressants mention may be made of polymethacrylate based
polymers. The amount thereof added may be within the range of 0.01 to 5 parts by weight
relative to 100 parts by weight of base oil.
[0052] Defoaming agents may also be added in order to impart foaming resistance to the lubricating
oil composition of the present invention. As examples of defoaming agents suitable
for the present invention mention may be made of dimethylpolysiloxane, organosilicates
such as diethylsilicate and fluorosilicones, and non-silicone defoaming agents such
as polyalkylacrylates. The amount thereof added may be within the range of from 0.0001
to 0.1 part by weight relative to 100 parts by weight of base oil.
[0053] For demulsifiers suitable for the present invention mention may be made of those
of the known art normally used as lubricating oil additives. The amount thereof added
may be within the range of from 0.0005 to 0.5 part by weight relative to 100 parts
by weight of base oil.
Examples
[0054] The invention is explained in more detail below by means of Examples and Comparative
Examples, but the invention is not limited to these Examples.
[0055] The following materials were used in preparing the Examples and Comparative Examples.
1. Base oils
[0056]
(1-1) Base Oil 1: A paraffinic mineral oil obtained by a suitable combination of refining
procedures such as hydrocracking and dewaxing of a lubricating oil fraction obtained
by atmospheric distillation of crude oil. Categorised as Group II (Gp II) according
to the API (American Petroleum Institute) base oil categories.
(Characteristics: kinetic viscosity at 100°C: 5.35 mm2/s; kinetic viscosity at 40°C: 31.4 mm2/s; viscosity index: 103; density at 15°C: 0.864; sulphur content (as converted to
elemental sulphur): less than 10 ppm; nitrogen content (as converted to elemental
nitrogen): less than 1 ppm; aniline point: 110°C; ring-analysis paraffin content as
determined by ASTM D3238: 62%; ditto naphthene content: 38%; ditto aromatic content:
less than 1%; initial boiling point based on gas chromatography distillation as determined
by ASTM D5480: 312°C)
(1-2) Base Oil 2: A paraffinic mineral oil obtained by a suitable combination of refining
procedures such as hydrocracking and dewaxing of a lubricating oil fraction obtained
by atmospheric distillation of crude oil. Categorised as Group III (Gp III) according
to the API (American Petroleum Institute) base oil categories.
(Characteristics: kinetic viscosity at 100°C: 6.57 mm2/s; kinetic viscosity at 40°C: 37.5 mm2/s; viscosity index: 130; density at 15°C: 0.823; sulphur content (as converted to
elemental sulphur): less than 10 ppm; nitrogen content (as converted to elemental
nitrogen): less than 1 ppm; aniline point: 130°C; ring-analysis paraffin content as
determined by ASTM D3238: 78%; ditto naphthene content: 22%; ditto aromatic content:
less than 1%; polycyclic aromatic content according to IP 346: 0.2%)
(1-3) Base Oil 3: A GTL oil synthesised by the Fischer-Tropsch method and categorised
as Group III according to the API (American Petroleum Institute) base oil categories.
(Characteristics: kinetic viscosity at 100°C: 5.10 mm2/s; kinetic viscosity at 40°C: 23.5 mm2/s; viscosity index: 153; density at 15°C: 0.821; sulphur content (as converted to
elemental sulphur): less than 10 ppm; nitrogen content (as converted to elemental
nitrogen): less than 1 ppm; ring-analysis aromatic content as determined by ASTM D3238:
less than 1%)
(1-4) Base Oil 4: A poly-a-olefin synthetic oil, generally known as PAO6 and categorised
as Group IV according to the API (American Petroleum Institute) base oil categories.
(Characteristics: kinetic viscosity at 100°C: 5.89 mm2/s; kinetic viscosity at 40°C: 31.2 mm2/s; viscosity index: 135; density at 15°C: 0.827; sulphur content (as converted to
elemental sulphur): less than 10 ppm; nitrogen content (as converted to elemental
nitrogen): less than 1 ppm; aniline point: 128°C; ring-analysis aromatic content as
determined by ASTM D3238: less than 1%; initial boiling point based on gas chromatography
distillation as determined by ASTM D5480: 403°C)
(1-5) Base Oil 5: A paraffinic mineral oil obtained by a suitable combination of refining
procedures such as dewaxing of a lubricating oil fraction obtained by atmospheric
distillation of crude oil. Categorised as Group I (Gp I) according to the API (American
Petroleum Institute) base oil categories. (Characteristics: kinetic viscosity at 100°C:
4.60 mm2/s; kinetic viscosity at 40°C: 24.6 mm2/s; viscosity index: 101; density at 15°C: 0.866; sulphur content (as converted to
elemental sulphur): 460 ppm; nitrogen content (as converted to elemental nitrogen):
20 ppm; aniline point: 110°C; ring-analysis paraffin content as determined by ASTM
D3238: 66%; ditto naphthene content: 31%; ditto aromatics content: 3%; aniline point:
99°C; polycyclic aromatic content according to IP 346: 0.8%; initial boiling point
based on gas chromatography distillation as determined by ASTM D5480: 331°C)
2. Additives
[0057]
(2-1) Additive A1: Aspartic acid derivative: K-CORR100, manufactured by King Co. Ltd.,
acid number according to the method of JIS K2501: 100 mgKOH/g
(2-2) Additive A2: Aspartic acid derivative: MONACOR 39, manufactured by Unichema
Co. Ltd., acid number according to the method of JIS K2501: 60 mgKOH/g
(2-3) Additive B1: Epoxidised rapeseed fatty acid isobutyl ester
(2-4) Additive B2: Epoxidised rapeseed fatty acid 2-ethylhexyl ester
(2-5) Additive B3: Epoxidised linseed fatty acid butyl ester
(2-6) Additive B4: Epoxidised soybean oil
(2-7) Additive C1: Coconut amine (main constituent dodecylamine); primary amine compound
of primary alkyl, base number according to the method of JIS K2501: 390 mgKOH/g.
(2-8) Additive C2: Oleylamine; primary alkyl primary amine compound, base number according
to the method of JIS K2501: 215 mgKOH/g.
(2-9) Additive C3: Beef tallow amine (main constituents oleylamine, stearylamine,
palmitylamine); primary alkyl primary amine compound, base number according to the
method of JIS K2501: 215 mgKOH/g.
(2-10) Additive C4: Primary amine with C18 tertiary alkyl group; tertiary alkyl primary
amine compound, base number according to the method of JIS K2501: 155 mgKOH/g.
(2-11)Additive C5: Coconut diamine (main constituent dodecyldiamine); primary alkyl
primary diamine compound, base number according to the method of JIS K2501: 440 mgKOH/g.
(2-12) Additive C6: Coconut secondary amine (main constituent didodecylamine); primary
alkyl secondary amine compound, base number according to the method of JIS K2501:
160 mgKOH/g.
(2-13) Other additives: The compounds shown below were mixed in: diphenylamine, phenylnaphthylamine,
benzenepropanoic acid 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester, N,N-bis(2-ethylhexyl)-(4 or 5)-methyl-1H-benzotriazole-1-methylamine,
triallyl phosphate, 3-(di-isobutoxythiophosphorylsulphanyl)-2-methyl-propionic acid,
pentaerythritol ester, polymethacrylate-type pour-point depressant, dimethylpolysiloxane-type
defoaming agent, and polyoxyethylene·polyoxypropylene glycol-type demulsifier.
Examples 1 to 21, Comparative Examples 1 to 7
[0058] Using the aforementioned materials, the lubricating oil compositions of Examples
1 to 21 and Comparative Examples 1 to 7 were prepared in accordance with the compositions
shown in Tables 1 to 7.
Tests
[0059] Corrosion prevention tests and thermal stability tests were carried out as below
on the lubricating oil compositions of Examples 1 to 21 and Comparative Examples 1
to 7 in order to see how they performed. Pendulum tests for friction coefficient were
also carried out.
Corrosion prevention test
[0060] In accordance with JIS K2510, 300 ml of the oil being tested was tapped off into
a container disposed inside a constant temperature bath, and stirred at a speed of
1000 revolutions per minute. When the temperature reached 60°C, an iron test-piece
was inserted into the test oil, and 30 ml of artificial sea water was further added.
The temperature was maintained at 60°C while stirring continuously for 24 hours. The
test-piece was then removed and assessed by eye for the presence of any rust. If no
rust occurred, the oil was deemed to have passed.
Thermal stability test
[0061] In accordance with Thermal Stability Test Procedure 'A' of Cincinnati Milacron Inc.,
200 ml of the oil being tested was tapped off into a container disposed inside a constant
temperature bath, and left there for 168 hours at 125°C in the joint presence of a
copper catalyst and an iron catalyst. Then, after cooling to room temperature, the
sludge was gathered by a 5-micron filter and the amount of sludge generated was weighed.
The figures in the tables are the amount of sludge per 200 ml of test oil (mg/200
ml).
[0062] The evaluation of the tests was made according to the following criteria:
| Amount of sludge generated less than 2.0 mg |
Ø (Excellent) |
| Amount of sludge generated 2.0 to less than 10.0 mg |
○ (Good) |
| Amount of sludge generated 10.0 mg or more |
X (Fail) |
Pendulum test, friction coefficient
[0063] The friction coefficient at 25°C was measured using a Masuda pendulum-type oiliness
tester manufactured by Shinko Machine Manufacturing Co. Ltd. In this test the oil
being tested is supplied to the friction portion of the pendulum fulcrum, the pendulum
is made to move, and the friction coefficient is obtained from the reduction in oscillations.
[0064] The evaluation of the tests was made according to the following criteria:
| Friction coefficient 0.135 or less |
Ø (Excellent) |
| Friction coefficient 0.136 to less than 150 |
○ (Good) |
| Friction coefficient 0.150 or more |
X (Fail) |
Test results
[0065] The results of the tests are shown in Tables 1 to 7.
Discussion
[0066] As is clear from the results in Tables 1, 2 and 6, when the aspartic acid derivative
of Comparative Example 2 (Additive A1) was added, it had adequate corrosion resistance
but the amount of sludge generated in the thermal stability test was large. However,
it was possible to reduce the amount of sludge while having adequate corrosion resistance
by also using an epoxidised ester compound (Additive B1 or B2) as in Examples 1 to
3 and Example 8. Further, if the amount of epoxidised ester (Additive B1) incorporated
was increased, the amount of sludge decreased and the sludge inhibition effect was
more marked, as shown by Examples 1 to 3. Furthermore, as shown by Examples 1 to 6,
the amount of sludge was small in lubricating oil compositions using any of the highly
refined base oils 1 to 4, and in particular in the case of using the highly refined
base oils shown in Examples 4 to 6, the amount of sludge was extremely small (Ø :
excellent), and the sludge inhibition effect was even greater.
[0067] Similarly, as between Example 7 (Table 2) and Comparative Example 3 (Table 6), superior
corrosion resistance and a superior sludge inhibition effect were obtained by using
an aspartic acid derivative (Additive A2) together.with an epoxidised ester compound
(Additive B1) in the base oil. Also, when looking at Example 9 (Table 2), the excellent
corrosion resistance and excellent sludge inhibition effect of the aforementioned
aspartic acid derivative and epoxidised ester compound were demonstrated even when
using other additives with them.
[0068] In Examples 10 to 13 (Table 3), the sludge inhibition was even further improved by
further using an aliphatic amine compound (Additive C1) in the base oil in addition
to the aspartic acid derivative and epoxidised ester compound, and, given that the
friction coefficient was considerably lower than in Comparative Examples 1 to 6 (Table
6), excellent low friction characteristics were demonstrated. In particular, when
using Base Oil 3 (Example 12) and Base Oil 4 (Example 13), it was possible to make
the friction coefficient considerably lower through the combination of these additives
(Ø : excellent), and it was accordingly possible to impart excellent energy saving
characteristics to the lubricating oil composition.
[0069] Also, in the case both of the aspartic acid derivative (Additive A2) used in Example
14 (Table 4) and of the epoxidised ester compound (Additive B2 or B3) used in Examples
15 to 16 (Table 4) excellent corrosion resistance, excellent sludge inhibition and
excellent low friction characteristics were similarly obtained.
[0070] In the case of Examples 17 to 21 (Table 5), with various aliphatic amine compounds
(Additives C2 to 6), excellent corrosion resistance, excellent sludge inhibition and
excellent low friction characteristics were demonstrated through the combination of
an aspartic acid derivative and epoxidised ester compound. In particular, a considerable
sludge inhibition effect was obtained for Example of Embodiment 19 using an aliphatic
amine compound (Additive C4). Also, in the case of Examples of Embodiment 17, 18 and
20 using aliphatic amine compounds (Additives C2, C3, C5), it was possible to reduce
the friction coefficient considerably (Ø : excellent) and it was accordingly possible
to impart excellent energy saving characteristics to the lubricating oil compositions.