(19)
(11) EP 0 735 128 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
23.08.2000 Bulletin 2000/34

(21) Application number: 96302164.7

(22) Date of filing: 28.03.1996
(51) International Patent Classification (IPC)7C10M 141/08, C10M 141/10
// (C10M141/08, 133:12, 135:18),(C10M141/10, 133:12, 135:18, 137:02), C10N30:10, C10N30:12, C10N40:00

(54)

Extended life rust and oxidation oils

Korrosions- und Oxidationsöle mit verlängerter Lebensdauer

Des huiles de corrosion et d'oxidation à vie prolongée


(84) Designated Contracting States:
BE GB

(30) Priority: 28.03.1995 US 413038

(43) Date of publication of application:
02.10.1996 Bulletin 1996/40

(73) Proprietor: ETHYL CORPORATION
Richmond Virginia 23217 (US)

(72) Inventor:
  • Iyer, Ramnath
    Midlothian, Virginia 23113 (US)

(74) Representative: Cresswell, Thomas Anthony 
J.A. KEMP & CO. 14 South Square Gray's Inn
London WC1R 5LX
London WC1R 5LX (GB)


(56) References cited: : 
EP-A- 0 528 610
US-A- 3 230 168
US-A- 4 125 479
US-A- 5 236 610
GB-A- 810 741
US-A- 4 119 551
US-A- 4 226 732
   
     
    Remarks:
    The file contains technical information submitted after the application was filed and not included in this specification
     
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    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 R4 is a hydrocarbylene group having 1 to 10 carbon atoms, each R5 is a hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms, and each R3 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

            (R6O)3P

    where each R6 is independently C1 to C18 alkyl, C2 to C18 alkenyl, or C6 to C18 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 R4 is a hydrocarbylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Preferably, R4 is an alkylene group, most preferably a methylene or ethylene group. Each R5 is a hydrogen or a hydrocarbyl group having 1 to 18 carbon atoms, preferably 2 to 10, more preferably 2 to 6. Each R3 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 R1 and R2 are independently hydrogen or C1 to C18 alkyl. For purposes herein, "alkylphenyl-α-naphthylamine" includes phenyl-α-naphthylamine (PANA), where both R1 and R2 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:

            (R6O)3P

    where each R6 is independently C1 to C18 alkyl, C2 to C18 alkenyl, or C6 to C18 aryl. In preferred compounds, each R6 is independently C3 to C12 alkyl or C6 to C18 aryl. In most preferred compounds, R6 is C6 to C18 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 R7 is hydrogen or an alkyl group with 1 to 4 carbons, R8 is an alkyl group with 1 to 4 carbons or a benzylic group, and R9 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, R7 is hydrogen, R8 is an alkyl group with 1 to 4 carbons, and R9 is an alkyl group with 1 to 6 carbons; most preferably both R8 and R9 are t-butyl. In a second example R9 is hydrogen, R7 is an alkyl group with 1 to 4 carbons, and R8 is an alkyl group with 1 to 4 carbons; most preferably both R7 and R8 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



    Claims

    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.


     


    Ansprüche

    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.
     


    Revendications

    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.