BACKGROUND OF THE INVENTION
1. Field of the Invention.
[0001] This invention relates to the field of improved thermal and oxidative stability of
lubricating fluids.
2. Description of the Prior Art.
[0002] Lubricating oils such as circulating oils, turbine oils, hydraulic fluids and transformer
oils as well as others require good oxidation stability and good rust inhibition properties.
Extended life for such fluids where desired rust and oxidation (R&O) inhibition properties
are maintained for extended periods of use is demanded by industrial users and provides
important economic benefit. R&O oils are widely used in turbine and compressor circulating
systems. Their thermal and oxidative stability are of particular importance. In addition,
R&O oils provide rust protection, corrosion protection and metal passivation. Antiwear
protection is sometimes needed.
[0003] GB 810,741 describes lubricating oil compositions which are said to exhibit increased
oxidation resistance. The compositions contain a) a secondary aromatic mono- or polyamine
in which the nitrogen atom is attached directly to two aromatic radicals and b) an
alkyl ester of a dithiocarbamic acid.
[0004] USP 3,230,168 describes lubricants which are said to have good oxidation stability.
These lubricants contain an aryl amine in combination with an amine salt of a N-substituted
dithiocarbamic acid.
[0005] EP-A-528610 describes low phosphorus engine oils containing an alkylthiocarbamate.
The oils may also contain other additives.
[0006] USP 5,236,610 describes an antioxidant additive for lubricants. As principal component
the additive contains a substituted phenolic carboxylic acid tetraester of pentaerythritol.
The additive may also include additional antioxidants.
[0007] U. S. Patent 4,125,479 to Chesluk et al. discloses an oxidation inhibited lubricating
oil with a combination of additives comprising methylenebis(di-n-butyldithiocarbamate)
and 4-methyl-2,6-ditertiary butyl phenol, said to provide enhanced oxidation inhibition.
U. S. Patent 4,880,551 to Doe discloses an antioxidant composition consisting of a
1-(di(4-octylphenyl) aminomethyl)tolutriazole and at least one antioxidant selected
from the group consisting essentially of methylenebis(di-n-butyldithiocarbamate);
2,6-di-t-butyl-4-sec-butylphenol; 2,6-di-t-butyl-4-methylphenol and butylated phenol
mixture. International PCT Publication Number WO 92/19703, published 12 November 1992,
to Lubrizol Corporation discloses thermally stable lubricant and functional fluid
compositions containing hydrocarbyl phosphite in combination with at least one basic
alkali or alkaline earth metal salt of an acidic organic compound and a metal deactivator,
the composition may additionally contain a dithiocarbamate compound for an antiwear
agent. These references do not teach or suggest the combination of components claimed
herein.
[0008] There is an increasing demand for inhibited oils with extended lifetimes. R&O lubricant
concentrate packages typically contain phenolic, amino and other antioxidants, rust
inhibitor(s), a metal deactivator, and a demulsifying agent. They may include additional
components such as an antiwear agent depending on the final performance properties
desired. The principle function of the antioxidants is the inhibition of oxidative
degradation of R&O oils that are obtained by blending the R&O lubricant concentrate
package in a particular basestock oil of choice. Basestock oils have varying degrees
of thermal and oxidative stability.
[0009] This invention will serve to improve the thermal and oxidative properties of even
those basestock oils that are known to have less than satisfactory stability. The
current invention relates to the use of certain components. that contribute directly
to prolonging the life of R&O oils.
SUMMARY OF THE INVENTION
[0010] In a rust and oxidation (R&O) inhibited lubricant composition comprising a base oil
and rust and oxidation inhibitors, the invention is directed to the improvement wherein
said lubricant composition comprises up to 1.0 weight % of (a) a dithiocarbamate compound
represented by the formula

wherein R
4 is a hydrocarbylene group having 1 to 10 carbon atoms, each R
5 is a hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms, and each R
3 is a hydrocarbyl group having 1 to 18 carbon atoms; and up to 0.15 weight % of (b)
an alkylphenyl-α-naphthylamine. The lubricant composition further optionally comprises
up to 0.75 weight % of (c) a hydrocarbyl phosphite represented by the formula
(R
6O)
3P
where each R
6 is independently C
1 to C
18 alkyl, C
2 to C
18 alkenyl, or C
6 to C
18 aryl. Each component (a) and (b), or (a), (b) and (c) is present in an amount sufficient
to provide improved inhibition of oxidation to the R&O lubricant composition.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0011] The additive combinations of this invention may be used in any lubricating oil where
oxidation inhibition is required. This may include circulating oils used in compressor
and turbine circulating systems, transformer oils, engine oils and other oils which
are subjected to conditions where oxidation is a problem. It has been found that a
dithiocarbamate compound in combination with an alkylphenyl-α-naphthylamine, in effective
amounts, and that combination in further combination with an effective amount of hydrocarbyl
phosphite, provide important and unexpected enhancement of thermal and oxidation stability,
with resulting improvement in the life of the R&O oil.
[0012] The additive combinations of this invention can be incorporated in a wide variety
of lubricants and functional fluids in effective amounts to provide suitable active
ingredient concentrations. The base oils useful herein can be hydrocarbon oils of
suitable viscosities; synthetic oils such as hydrogenated polyolefin oils; poly-α-olefin
oligomers (such as hydrogenated poly-1-decene); alkyl esters of dicarboxylic acids;
complex esters of dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic
or phosphoric acids; polysilicones; fluorohydrocarbon oils; and mixtures of mineral,
natural and/or synthetic oils in any proportion, etc. The term "base oil" for this
disclosure includes all the foregoing and mixtures thereof.
[0013] The dithiocarbamate compound to be included in the combination of the invention is
represented by the formula

wherein R
4 is a hydrocarbylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
Preferably, R
4 is an alkylene group, most preferably a methylene or ethylene group. Each R
5 is a hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms, preferably 2 to
10, more preferably 2 to 6. Each R
3 is a hydrocarbyl group having 1 to 18 carbon atoms, preferably 2 to 10, more preferably
2 to 6. A commercially available dithiocarbamate compound appropriate for use in the
invention is VANLUBE° 7723, methylenebis(di-n-butyldithiocarbamate).
[0014] Beyond a certain level, the dithiocarbamate compound may start hurting or interfering
with relevent bench tests other than R&O tests. Higher levels of dithiocarbamate compound
may result in deterioration of thermal stability, causing undesired sludge in thermal
stability tests. Also rust problems may occur at higher dithiocarbamate compound levels,
which may result in failure of specified rust tests. An effective amount of dithiocarbamate
compound is up to 1.0 weight percent of the finished lubricant composition, for example
0.01 to 1.0 weight percent, 0.02 to 0.5 preferred, 0.03-0.2 most preferred.
[0015] The alkylphenyl-α-naphthylamine for use in the invention is represented by the formula

wherein R
1 and R
2 are independently hydrogen or C
1 to C
18 alkyl. For purposes herein, "alkylphenyl-α-naphthylamine" includes phenyl-α-naphthylamine
(PANA), where both R
1 and R
2 are hydrogen. An effective amount of alkylphenyl-α-naphthylamine for use in the invention
is up to 0.15 weight percent of the finished lubricant composition, for example 0.025
to 0.15 weight percent, 0.03 to 0.125 weight percent preferred.
[0016] The hydrocarbyl phosphite compound for use in the invention is represented by the
formula:
(R
6O)
3P
where each R
6 is independently C
1 to C
18 alkyl, C
2 to C
18 alkenyl, or C
6 to C
18 aryl. In preferred compounds, each R
6 is independently C
3 to C
12 alkyl or C
6 to C
18 aryl. In most preferred compounds, R
6 is C
6 to C
18 aryl, including triphenylphosphite, tricresylphos-phite, trinonylphenylphosphite
(C15), tridodecylphenylphosphite, and mixtures thereof. An effective amount of the
hydrocarbyl phosphite compound for use in the invention is up to 0.075 weight percent
of the finished lubricant composition, for example 0.005 to 0.075 weight percent,
0.01 to 0.06 preferred.
[0017] R&O oils will typically contain a conventional quantity of one or more antioxidants
in order to protect the composition from premature degradation in the presence of
air, especially at elevated temperatures. Typical antioxidants include various alkylated
phenols, hindered phenols and phenol derivatives such as t-butyl hydroquinone, butylated
hydroxyanisole, polybutylated bisphenol A, butylated hydroxy toluene, alkylated hydroquinone,
2,5-ditertaryl hydroquinone; 2,6-ditert-butyl-para-cresol; 2,2'-methylenebis(6-tert-butyl-p-cresol);
1,5-naphthalenediol; 4,4'-thiobis(t-tert-butyl-m-cresol); p,p-biphenol; 4,4'-butylidenebis(6-tert-butyl-m-cresol);
4-methoxy-2,6-di-tert-butylphenol; and the like; also amino antioxidants such as aldehyde
amines, ketone amines, ketone-diarylamines, alkylated diphenylamines, phenylenediamines,
and the phenolic amines; secondary aromatic amine antioxidants, sulfurized phenolic
antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and
the like as well as mixtures of antioxidants. Phenolic antioxidants are known and
may be represented by the general formula:

where R
7 is hydrogen or an alkyl group with 1 to 4 carbons, R
8 is an alkyl group with 1 to 4 carbons or a benzylic group, and R
9 is hydrogen, an alkyl group with 1 to 6 carbons, or an alkoxy group with 1 to 6 carbons.
In one example of a phenolic antioxidant for use with the invention, R
7 is hydrogen, R
8 is an alkyl group with 1 to 4 carbons, and R
9 is an alkyl group with 1 to 6 carbons; most preferably both R
8 and R
9 are t-butyl. In a second example R
9 is hydrogen, R
7 is an alkyl group with 1 to 4 carbons, and R
8 is an alkyl group with 1 to 4 carbons; most preferably both R
7 and R
8 are t-butyl.
[0018] The R&O oil compositions useful herein will also typically comprise a rust inhibitor
and a metal deactivator. These are commonly selected from alkenyl succinic acid esters
and from triazoles and triazole derivatives, known for these purposes.
[0019] It is also useful to this invention to employ in the lubricant compositions and additive
concentrates a suitable quantity of a corrosion inhibitor. This may be a single compound
or a mixture of compounds having the property of inhibiting corrosion of metallic
surfaces. One type of such additives are inhibitors of copper corrosion. Such compounds
include thiazoles, triazoles and thiadizoles. Examples of such compounds include benzotriazole,
tolytriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzothiazole,
2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles,
2-mercapto-5-hydrocarbyldithio-1, 3, 4-thiadiazoles, 2, 5-bis(hydrocarbylthio)-1,
3, 4-thiadiazoles, and 2, 5-(bis)hydrocarbyldithio), 1, 3, 4-thiadiazoles. The preferred
compounds are the 1, 3, 4-thiadiazoles, a number of which are available as articles
of commerce. Such compounds are generally synthesized from hydrazine and carbon disulfide
by known procedures. See for example U.S. Pat. Nos. 2,765,289; 2,749, 311; 2,760,933;
2,850,453; 2,910,439; 3,663,561; 3,862,798; and 3,840,549. Other types of corrosion
inhibitors are known and suitable for use in the compositions of this invention. Suitable
corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated
compounds such as ethoxylated amines, ethoxylated and/or propoxylated phenols, and
ethoxylated alcohols; imidazolines; and the like. Materials of these types are well
known to those skilled in the art and a number of such materials are available as
articles of commerce.
[0020] The lubricating composition of the present invention may further contain other additives
such as extreme pressure agents and/or antiwear agents.
[0021] The additives of the present invention can be incorporated into a lubricating oil
in any convenient way. The compounds, or mixtures thereof, can be added directly to
the oil at the desired level or by adding concentrates of the additive to the oil.
Accordingly, the additive compounds can be blended with a suitable oil soluble solvent
such as mineral spirits and/or base oil to form a concentrate and then the concentrate
may be blended with lubricating oil to obtain a final formulation. A complete R&O
lubricant concentrate package can be prepared containing antioxidants, rust inhibitor,
metal, deactivator, demulsifier, additional desired components as well as the components
of the invention, i.e. the dithiocarbamate compound and the alkylphenyl-α-naphthylamine
compound; or the dithiocarbamate compound, the alkylphenyl-α-naphthylamine compound,
and the hydrocarbyl phosphite. The components are present in the lubricant concentrate
package at a level sufficient to provide an effective level in the finished composition
to provide the enhanced oxidation inhibition properties.
EXAMPLES
[0022] The following tests were performed to demonstrate the advantages of the invention:
(a) The American Society for Testing and Materials (ASTM) provides a Standard Test
Method for Oxidation Characteristics of Inhibited Mineral Oils (ASTM D943-81(Reapproved
1991)). The D943 test method was developed for, and is used to evaluate the oxidation
stability of inhibited steam turbine oils and other oils containing R&O inhibitors
in the presence of oxygen, water, and copper and iron metals at an elevated temperature
and is considered of value in the industry in estimating the oxidation stability of
lubricants, especially those that are prone to water contamination.
(b) ASTM D-2272-85(Reapproved 1991), Standard Test Method for Oxidation Stability
of Steam Turbine Oils by Rotating Bomb, (RBOT) utilizes an oxygen-pressured bomb to
evaluate the oxidation stability of new and in service turbine oils having the same
composition (base stock and additives) in the presence of water and a copper catalyst
coil at 150°C.
(c) The Cincinnati Milacron Thermal Stability Test procedure "A" (CM "A") is intended
to check the thermal stability of a designated oil sample by immersing copper and
iron rods into an oil sample, heating in an oil bath or oven (135-138° C) for one
week (168 hours), and determining the weight of resulting residue or "sludge".
[0023] HiTec 575® Ashless Rust & Oxidation Inhibitor is a lubricant additive concentrate
package commercially available from Ethyl Corporation. This is fully formulated for
high-performance, turbine-quality hydraulic fluids. It provides extended oxidation
life, excellent rust control, demulsibility and filterability, and is compatible with
other additives commonly used in hydraulic fluids. HiTec 575 lubricant additive represents
a typical R&O package and has been used in the studies reported herein to demonstrate
the improved oxidation properties obtained with the present invention. Texaco ISO
46 basestock oil was used in preparing the formulation of the examples below. In Example
1, HiTec 575 lubricant additive was blended with the basestock oil at its recommended
dosage, 0.80 weight percent. HiTec 575 lubricant additive contains PANA in an amount
that provides 0.10 weight percent to the blended lubricant composition at this recommended
dosage. For Examples 2 through 6 below, the PANA was removed from the HiTec 575 lubricant
additive. The HiTec 575 lubricant additive without PANA was blended with the Texaco
ISO 46 basestock oil at 0.80 weight percent dosage, and the dithiocarbamate compound
and triphenylphosphite were added in the amounts indicated. For Examples 7 through
14, commercially available HiTec 575 lubricant additive was blended with the basestock
at 0.80 weight percent dosage, and the dithiocarbamate compound and triphenylphosphite
were added in the amounts indicated. A commercially available dithiocarbamate compound,
VANLUBE° 7723, methylenebis(di-n-butyldithiocarbamate), was used in the Examples in
the amounts indicated. Table I below provides the composition of Examples 1-11 and
the results of D943 and RBOT testing and CM "A" Sludge testing. The composition and
the results of RBOT testing for Examples 12-14 are also provided in Table I.
TABLE I
Example |
PANA wt % |
DITHIOCARBAM. wt % |
TPP wt % |
RBOT minutes |
CM "A" SLUDGE mg/100ml |
D943 hours |
1 |
0.10 |
- |
- |
745 |
14.00 |
2644 |
2 |
- |
- |
- |
708 |
14.03 |
2634 |
3 |
- |
0.025 |
- |
765 |
9.92 |
2756 |
4 |
- |
0.025 |
0.025 |
775 |
19.5 |
2523 |
5 |
- |
0.050 |
- |
805 |
12.25 |
2922 |
6 |
- |
0.050 |
0.025 |
826 |
20.08 |
2526 |
7 |
0.10 |
0.025 |
0.025 |
945 |
23.05 |
2724 |
8 |
0.10 |
0.050 |
0.025 |
1048 |
22.10 |
3852 |
9 |
0.10 |
0.050 |
0.050 |
986 |
25.40 |
3684 |
10 |
0.10 |
0.100 |
0.025 |
1130 |
19.75 |
〉 3700* |
11 |
0.10 |
0.100 |
0.050 |
1195 |
29.03 |
3850 |
12 |
0.10 |
0.05 |
- |
942 |
|
|
13 |
0.10 |
0.10 |
- |
1080 |
|
|
14 |
0.10 |
0.20 |
- |
1335 |
|
|
* Test still running at time of filing |
1. A lubricant composition comprising a base oil, rust and oxidation inhibitors and
a) up to 1.0 weight% of (a) a dithiocarbamate of formula (I)

wherein R4 is a hydrocarbylene group having 1 to 10 carbon atoms, the groups R5 are the same or different and each is hydrogen or a hydrocarbyl group having 1 to
18 carbon atoms, and the groups R3 are the same or different and each is a hydrocarbyl group having 1 to 18 carbon atoms;
b) up to 0.15 weight% of (b) an alkylphenyl-α-naphthylamine of formula (II)

wherein R1 and R2 are the same or different and each is hydrogen or C1 to C18 alkyl; and optionally
c) up to 0.075 weight% of (c) a hydrocarbyl phosphite of formula (III)
(R6O)3P (III)
wherein the groups R6 are the same or different and each is C1 to C18 alkyl, C2 to C18 alkenyl, or C6 to C18 aryl.
2. A composition according to claim 1 wherein in the dithiocarbamate compound (a), R4 is an alkylene group having 1 to 4 carbon atoms, each R5 is hydrogen or a hydrocarbyl group having 2 to 10 carbon atoms, and each hydrocarbyl
group R3 has 2 to 10 carbon atoms.
3. A composition according to claim 2 wherein both groups R5 are hydrogen and each group R3 has 2 to 6 carbon atoms.
4. A composition according to claim 1 wherein the dithiocarbamate compound (a) is methylenebis(di-n-butyldithiocarbamate).
5. A composition according to any one of the preceding claims wherein each R6 is independently C3 to C12 alkyl or C6 to C18 aryl.
6. A composition according to claim 5 wherein the hydrocarbyl phosphite compound (c)
is triphenylphosphite or tricresylphosphite.
7. A composition according to any one of claims 1 to 6 comprising from 0.01 to 1.0 weight%
of the dithiocarbamate (a) and from 0.025 to 0.15 weight% of the alkylphenyl-α-naphthylamine
(b).
8. A composition according to any one of claims 1 to 6 comprising from 0.01 to 1.0 weight%
of the dithiocarbamate (a), from 0.025 to 0.15 weight% of the alkylphenyl-α-naphthylamine
(b), and from 0.005 to 0.075 weight% of the hydrocarbyl phosphite (c).
9. A composition according to claim 8 wherein the dithiocarbamate (a) is present in an
amount of 0.02 to 0.5 weight%, the alkylphenyl-α-naphthylamine (b) is present in an
amount of 0.03 to 0.125 weight%, and the hydrocarbyl phosphite (c) is present in an
amount of 0.01 to 0.06 weight%.
10. Use of a composition comprising up to 1.0 weight% of (a) a dithiocarbamate of formula
(I) as defined in claim 1, up to 0.15 weight% of (b) an alkylphenyl-α-naphthylamine
of formula (II) as defined in claim 1, and optionally up to 0.075 weight% of (c) a
hydrocarbyl phosphite of formula (III) as defined in claim 1 for improving the inhibition
of oxidation of a lubricant composition containing rust and oxidation inhibitors.
11. A lubricant additive concentrate for formulation of rust and oxidation inhibited lubricant
compositions as defined in claim 1 comprising a base oil and rust and oxidation inhibitors,
the lubricant additive concentrate comprising
(a) a dithiocarbamate of formula (I) as defined in claim 1
(b) an alkylphenyl-α-naphthylamine of formula (II) as defined in claim 1,
and optionally (c) a hydrocarbyl phosphite of formula (III) as defined in claim 1,
components (a), (b) and, optionally (c), being present in an amount sufficient to
provide improved inhibition of oxidation to the rust and oxidation inhibited lubricant
composition.
1. Schmiermittelzusammensetzung, umfassend ein Basisöl, Rost- und Oxidationsinhibitoren
sowie
a) bis zu 1,0 Gew.-% (a) eines Dithiocarbamats der Formel (I)

in der R4 eine Hydrocarbylengruppe mit 1 bis 10 Kohlenstoffatomen ist, die Gruppen R5 gleich oder voneinander verschieden sind und jeweils Wasserstoff oder eine Hydrocarbylgruppe
mit 1 bis 18 Kohlenstoffatomen bedeuten und die Gruppen R3 gleich oder voneinander verschieden sind und jeweils eine Hydrocarbylgruppe mit 1
bis 18 Kohlenstoffatomen bedeuten;
b) bis zu 0,15 Gew.-% (b) eines Alkylphenyl-α-naphthylamins der Formel (II)

in der R1 und R2 gleich oder voneinander verschieden sind und jeweils Wasserstoff oder C1-C18-Alkyl bedeuten; sowie ggfs.
c) bis zu 0,075 Gew.-% (c) eines Hydrocarbylphosphits der Formel (III)
(R6O)3P (III),
in der die Gruppen R6 gleich oder voneinander verschieden sind und jeweils C1-C18-Alkyl, C2-C18-Alkenyl oder C6-C18-Aryl bedeuten.
2. Zusammensetzung nach Anspruch 1, in der in der Dithiocarbamatverbindung (a) R4 eine Alkylengruppe mit 1 bis 4 Kohlenstoffatomen ist, jedes R5 Wasserstoff oder eine Hydrocarbylgruppe mit 2 bis 10 Kohlenstoffatomen ist und jede
Hydrocarbylgruppe R3 2 bis 10 Kohlenstoffatome aufweist.
3. Zusammensetzung nach Anspruch 2, in der beide Gruppen R5 Wasserstoff sind und jede Gruppe R3 2 bis 6 Kohlenstoffatome hat.
4. Zusammensetzung nach Anspruch 1, in der die Dithiocarbamatverbindung (a) Methylenbis(di-n-butyldithiocarbamat)
ist.
5. Zusammensetzung nach einem der vorstehenden Ansprüche, in der jedes R6 unabhängig C3-C12-Alkyl oder C6-C18-Aryl ist.
6. Zusammensetzung nach Anspruch 5, in der die Hydrocarbylphosphitverbindung (c) Triphenylphosphit
oder Tricresylphosphit ist.
7. Zusammensetzung nach einem der Ansprüche 1 bis 6, die 0,01 bis 1,0 Gew.-% des Dithiocarbamats
(a) und 0,025 bis 0,15 Gew.-% des Alkylphenyl-α-naphthylamins (b) umfasst.
8. Zusammensetzung nach einem der Ansprüche 1 bis 6, die 0,01 bis 1,0 Gew.-% des Dithiocarbamats
(a), 0,025 bis 0,15 Gew.-% des Alkylphenyl-α-naphthylamins (b) und 0,005 bis 0,075
Gew.-% des Hydrocarbylphosphits (c) umfasst.
9. Zusammensetzung nach Anspruch 8, in der das Dithiocarbamat (a) in einer Menge von
0,02 bis 0,5 Gew.-%, das Alkylphenyl-α-naphthylamin (b) in einer Menge von 0,03 bis
0,125 Gew.-% und das Hydrocarbylphosphit (c) in einer Menge von 0,01 bis 0,06 Gew.-%
vorliegt.
10. Verwendung einer Zusammensetzung, die bis zu 1,0 Gew.-% (a) eines Dithiocarbamats
der Formel (I) wie in Anspruch 1 definiert, bis zu 0,15 Gew.-% (b) eines Alkylphenyl-α-naphthylamins
der Formel (II) wie in Anspruch 1 definiert und ggfs. bis zu 0,075 Gew.-% (c) eines
Hydrocarbylphosphits der Formel (III) wie in Anspruch 1 definiert enthält, um die
Oxidationshemmung einer Rost- und Oxidationsinhibitoren enthaltenden Schmiermittelzusammensetzung
zu verbessern.
11. Schmiermitteladditivkönzentrat zur Formulierung von Schmiermittelzusammensetzungen
mit Rost- und Oxidationshemmung wie in Anspruch 1 definiert, die ein Basisöl sowie
Rost- und Oxidationsinhibitoren umfassen, wobei das Schmiermitteladditivkonzentrat
(a) ein Dithiocarbamat der Formel (I) wie in Anspruch 1 definiert,
(b) ein Alkylphenyl-α-naphthylamin der Formel (II) wie in Anspruch 1 definiert sowie
ggfs.
(c) ein Hydrocarbylphosphit der Formel (III) wie in Anspruch 1 definiert
umfasst, wobei die Komponenten (a), (b) und ggfs. (c) in einer ausreichenden Menge
vorliegen, um die Oxidationshemmung der Schmiermittelzusammensetzung mit Rost- und
Oxidationshemmung zu verbessern.
1. Composition de lubrifiant comportant une huile de base, un inhibiteur de rouille et
un inhibiteur d'oxydation, et
a) jusque 1,0% en poids de (a) un dithiocarbamate de formule (I)

dans laquelle R4 est un groupe hydrocarbylène comptant de 1 à 10 atomes de carbone, les groupes R5 sont identiques ou différents et représentent chacun l'hydrogène ou un groupe hydrocarbyle
comptant de 1 à 18 atomes de carbone, et les groupes R3 sont identiques ou différents et représentent chacun un groupe hydrocarbyle comptant
de 1 à 18 atomes de carbone;
b) jusque 0,15% en poids de (b) une alkylphényl-α-naphtylamine de formule (II)

dans laquelle R1 et R2 sont identiques ou différents et représentent chacun l'hydrogène ou un alkyle en
C1 à C18; et facultativement
c) jusque 0,075% en poids de (c) un phosphite d'hydrocarbyle de formule (III):
(R6O)3P (III)
dans laquelle les groupes R6 sont identiques ou différents et représentent chacun un alkyle en C1 à C18, un alcényle en C2 à C18 ou un aryle en C6 à C18.
2. Composition selon la revendication 1, dans laquelle, dans le composé de dithiocarbamate
(a), R4 est un groupe alkylène comptant de 1 à 4 atomes de carbone, chaque R5 représente l'hydrogène ou un groupe hydrocarbyle comptant de 2 à 10 atomes de carbone
et chaque groupe hydrocarbyle R3 compte de 2 à 10 atomes de carbone.
3. Composition selon la revendication 2, dans laquelle les deux groupes R5 représentent l'hydrogène et chaque groupe R3 compte de 2 à 6 atomes de carbone.
4. Composition selon la revendication 1, dans laquelle le composé de dithiocarbamate
(a) est le méthylènebis(di-n-butyldithiocarbamate).
5. Composition selon l'une quelconque des revendications précédentes, dans laquelle chaque
R6 représente indépendamment un alkyle en C3 à C12 ou un aryle en C6 à C18.
6. Composition selon la revendication 5, dans laquelle le composé de phosphite d'hydrocarbyle
(c) est le phosphite de triphényle ou le phosphite de tricrésyle.
7. Composition selon l'une quelconque des revendications 1 à 6, comprenant de 0,01 à
1,0% en poids du dithiocarbamate (a) et de 0,025 à 0,15% en poids de l'alkylphényl-α-naphtylamine
(b).
8. Composition selon l'une quelconque des revendications 1 à 6, comprenant de 0,01 à
1,0% en poids du dithiocarbamate (a), de 0,025 à 0,15% en poids de l'alkylphényl-α-naphtylamine
(b) et de 0,005 à 0,075% en poids du phosphite d'hydrocarbyle (c).
9. Composition selon la revendication 8, dans laquelle le dithiocarbamate (a) est présent
en quantité de 0,02 à 0,5% en poids, l'alkylphényl-α-naphtylamine (b) est présente
en quantité de 0,03 à 0,125% en poids et le phosphite d'hydrocarbyle (c) est présent
en quantité de 0,01 à 0,06% en poids.
10. Utilisation d'une composition comprenant jusque 1,0% en poids de (a) un dithiocarbamate
de formule (I) comme défini dans la revendication 1, jusque 0,15% en poids de (b)
une alkylphényl-α-naphtylamine de formule (II) telle que définie dans la revendication
1 et facultativement jusque 0,075% en poids de (c) un phosphite d'hydrocarbyle de
formule (III) comme défini dans la revendication 1, pour améliorer l'inhibition de
l'oxydation d'une composition de lubrifiant contenant un inhibiteur de rouille et
un inhibiteur d'oxydation.
11. Concentré d'additif pour lubrifiant pour formulation de compositions de lubrifiant
à inhibition de la rouille et de l'oxydation telles que définies dans la revendication
1, comprenant une huile de base et des inhibiteurs de rouille et d'oxydation, le concentré
d'additif pour lubrifiant comprenant:
(a) un dithiocarbamate de formule (I) tel que défini dans la revendication 1,
(b) une alkylphényl-α-naphtylamine de formule (II) telle que définie dans la revendication
1, et
facultativement, (c) un phosphite d'hydrocarbyle de formule (III) tel que défini dans
la revendication 1, des composants (a), (b) et facultativement (c) étant présents
en quantité suffisante pour fournir une inhibition améliorée de l'oxydation à la composition
de lubrifiant protégée contre la rouille et l'oxydation.