EP0903399B1 - Lubricant compositions containing thiophosphoric and dithiophosphoric acid esters - Google Patents

Description

The invention relates to improved compositions with thiophosphoric acid esters and dithiophosphoric acid esters or phosphoric acid thioesters and the use of these lubricant compositions for improving the performance of lubricants, such as greases, metalworking, gear or hydraulic fluids.

The mentioned lubricants additives are added, which must meet demanding tasks, such as high load bearing capacity, wear and corrosion protection and antioxidant effect. Suitable for this purpose are zinc dialkyldithiophosphates which, however, the aim is to replace with metal-free compounds for reasons of environmental protection. In particular, in agriculture or in general in mobile hydraulic systems in which there is a risk of soil or water contamination with zinc compounds by leaks, the use of metal-free hydraulic fluids is required. There is therefore a need for metal-free and ashless additives. Suitable hydraulic fluids must also meet the specifications of the leading hydraulic machinery manufacturers, e.g. Denison HFO (Denison Hydraulics) or Vickers M-2980-S (Vickers) and be compatible with water. Furthermore, according to the specifications of DIN 51524 and Denison HFO, they should reach a fault load level (FLS) of at least 10 in the FZG test.

bekannt, welche unter dem Handelsnamen Irgalube^®63 (Warenzeichen der Ciba Spezialitätenchemie) kommerziell erhältlich sind.As oil additives for liquids are dithiophosphoric acid esters of the type:

known under the trade name Irgalube 63 ^® (trademark of Ciba Specialty Chemicals) are commercially available.

No. 5,531,911 discloses zinc-free hydraulic fluids containing phosphorus- and sulfur-containing additive components. One component is a thiophosphoric acid ester of the triphenylthiophosphate type (IRGALUBE TPPT). This is combined with Dithiophosphorsäureestern type IRGALUBE 63 and optional oil additive components, such as ammonium sulfonates.

Such formulations are disadvantageous because of their lack of compatibility with water. The contamination of a hydraulic oil with water is common, especially in mobile hydraulic systems. Because of the use of phosphorus and sulfur containing additives, hydrolytic degradation occurs to form corrosive decomposition products. which can attack the metals used in the hydraulic systems, eg steel and copper alloys, and cause damage to the hydraulic pumps. Also, agglomerations of these decomposition products may block the filters of Bypase filtration equipment. Since the service life of hydraulic systems can be significantly extended by ultrafine filtering, the filter mesh sizes of modern bypass filtration systems have been reduced from previously 30 μm to currently 6 μm. Therefore, only those hydraulic oils are to be used, which form only very small amounts of hydrolytic decomposition products when contaminated with water.

The present invention has for its object to produce compositions with improved compatibility with water, which have a much lower tendency to form undesirable Hydrolperodukten.

It has surprisingly been found that compositions with thiophosphoric acid esters combined with dithiophosphoric acid esters or phosphoric acid esters have a significantly lower tendency to form corrosive hydrolysis products and very good filtration properties by addition of a further additive component from the group of polyol partial esters, amines and epoxides in the event of contamination with water. By adding additional oil additives, eg. As ammonium phosphate esters, the load carrying capacity can be increased and reach FZG Fehierlaststufen ≥ 10.

1. a) ein Grundöl mit schmierender Viskosität;
2. b) mindestens einen Thiophosphorsäureester der Formel:
   
   worin R₁, R₂ und R₃ C₃-C₂₀-Kohlenwasserstoffreste darstellen; und
3. c) mindestens einen Dithiophosphorsäureester oder Phosphorsäurethioester der Formel:
   
   worin X Sauerstoff oder Schwefel und R₁, R₂ und R₃ unsubstituierte oder substituierte C₃-C₂₀-Kohlenwasserstoffreste darstellen; und
4. d) mindestens ein Öladditiv aus der Gruppe umfassend Polyolpartialester, Alkanolamine, Etheramine, primäre oder sekundäre Amine mit C₁-C₂₀Alkylresten, primären oder sekundären Amine mit C₂-C₂₀Alkylresten, die durch Hydroxy substituiert oder Sauerstoff unterbrochen sind, Polyoxyalkylendiamine, Polyoxyalkylenpolyamine, primäre oder sekundäre Amine mit C₅-C₆Cycloalkylresten und Epoxide.

The invention relates to compositions comprising:

1. a) a base oil with lubricating viscosity;
2. b) at least one thiophosphoric acid ester of the formula:
   
   wherein R ₁ , R ₂ and R _{3 represent} C ₃ -C ₂₀ hydrocarbon radicals; and
3. c) at least one dithiophosphoric acid ester or phosphoric acid thioester of the formula:
   
   wherein X represents oxygen or sulfur and R ₁ , R ₂ and R _{3 represent} unsubstituted or substituted C ₃ -C ₂₀ hydrocarbon radicals; and
4. d) at least one oil additive from the group comprising polyol partial esters, alkanolamines, etheramines, primary or secondary amines having C ₁ -C ₂₀ -alkyl radicals, primary or secondary amines having C ₂ -C ₂₀ -alkyl radicals which are substituted by hydroxyl or interrupted by oxygen, polyoxyalkylenediamines, Polyoxyalkylenepolyamines, primary or secondary amines with C ₅ -C ₆ cycloalkyl radicals and epoxides.

1. a) ein Grundöl mit schmierender Viskosität, welches man für Fette, Metallbearbeitungs-, Getriebe- und Hydraulikflüssigkeiten verwendet;
2. b) mindestens einen Thiophosphorsäureester der Formel I, worin R₁, R₂ und R₃ C₃-C₂₀-Kohlenwasserstoffreste darstellen;
3. c) mindestens einen Dithiophosphorsäureester der Formel II, worin X Schwefel und R₁, R₂ und R₃ unsubstituierte C₃-C₁₀-Kohlenwasserstoffreste oder worin R₁ und R₂ unsubstituierte C₃-C₁₀-Kohlenwasserstoffreste und R₃ einen substituierten C₃-C₁₀-Kohlenwasserstoffrest darstellen;
4. d) mindestens ein Öladditiv aus der Gruppe der Polyolpartialester, Amine und Epoxide;
5. e) ein Ammoniumphosphatester der Formel:
   
   worin R₁ und R₂ C₁-C₂₀-Kohlenwasserstoffreste und R_a, R_b, R_c und R_d unabhängig voneinander Wasserstoff oder C₁-C₂₀-Kohlenwasserstoffreste darstellen; und
6. f) übliche Öladditive.

A preferred embodiment relates to compositions comprising:

1. a) a lubricating viscosity base oil which is used for greases, metalworking, gear and hydraulic fluids;
2. b) at least one thiophosphoric acid ester of formula I wherein represent R _1, R ₂ and R ₃ is C ₃ -C ₂₀ hydrocarbon radicals;
3. c) at least one dithiophosphoric acid ester of the formula II in which X is sulfur and R ₁ , R ₂ and R _{3 are} unsubstituted C ₃ -C ₁₀ -hydrocarbon radicals or in which R ₁ and R _{2 are} unsubstituted C ₃ -C ₁₀ -hydrocarbon radicals and R _{3 is} a substituted C ₃ -C ₁₀ hydrocarbon radical;
4. d) at least one oil additive from the group of polyol partial esters, amines and epoxides;
5. e) an ammonium phosphate ester of the formula:
   
   wherein R ₁ and R _{2 are} C ₁ -C ₂₀ hydrocarbon radicals and R _a , R _b , R _c and R _{d are} independently hydrogen or C ₁ -C ₂₀ hydrocarbon radicals; and
6. f) usual oil additives.

A particularly preferred embodiment relates to compositions wherein the phosphorus content of the thiophosphoric acid ester component b), combined with the dithiophosphoric acid ester or phosphoric acid thioester component c), based on the composition comprising components a), b) and c), is less than 400 ppm ,

A most preferred embodiment relates to compositions wherein the phosphorus content of the thiophosphoric acid ester component b) combined with the dithiophosphoric acid ester or phosphoric acid thioester component c) and the ammonium phosphate ester component e) is less than 400 ppm based on the total composition.

The compositions are particularly suitable as multifunctional anti-wear additives - with additional antioxidant effect - for lubricants, such as greases, metalworking, gear or hydraulic fluids. They are largely metal and ash-free and meet the specifications mentioned. Surprisingly, mixtures of components b) and c) in the base oil a) give phosphorus concentrations of less than 400 ppm phosphorus very good anti-wear properties, ie very good VKA (test in Vierkugelapparat) and SRV (vibration friction wear) values. These mixtures have on the addition of the additive component from the group of Polyolialialester, amines and epoxides (component d)) in contamination with water very good filtration properties. By adding Further oil additives (components e) can achieve FZG fault load levels ≥ 10. Such blends meet the hydraulic machinery specifications of leading manufacturers, especially Denison HFO.

The terms and definitions used in the description of the present invention preferably have the following meanings:

Component a)

A base oil of lubricating viscosity is useful for the production of greases, metalworking, gear and hydraulic fluids.

Suitable greases, metalworking, gear and hydraulic fluids are based, for example, on mineral or synthetic oils or mixtures thereof. The lubricants are familiar to those skilled in the art and in the relevant literature, such as in Chemistry and Technology of Lubricants; Mortier, RM and Orszulik, ST (Editors); 1992 Blackie and Son Ltd. for GB, VCH Publishers NY for US, ISBN 0-216-92921-0, see pages 208 ff and 269 ff .; in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition 1969, J. Wiley & Sons, New York, Vol. 13, page 533 et seq. (Hydraulic Fluids); Performance Testing of Hydraulic Fluids; R. Tourret and EP Wright, Hyden & Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann's Encyclopedia of Ind. Chem., Fifth Completely Revised Edition, Verlag Chemie, DE-Weinheim, VCH Publishers for US, Vol. A 15, page 423 ff (lubricants), Vol. A 13, page 165 ff (hydraulic fluids) described.

The lubricants are in particular oils and fats, for example based on mineral oil or vegetable and animal oils, fats, tallow and wax or mixtures thereof. Vegetable and animal oils, fats, tallow and wax are, for example, palm kernel oil, palm oil, olive oil, rapeseed oil, rapeseed oil, linseed oil, soybean oil, cottonseed oil, sunflower oil, coconut oil, corn oil, castor oil, walnut oil and mixtures thereof, fish oils and their chemically modified, e.g. epoxidized and sulfoxidated, or genetically engineered forms, for example, genetically engineered soybean oil.

Examples of synthetic lubricants include aliphatic or aromatic carboxylic ester based lubricants, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly-α-olefins or silicones, the diacid diester with a monohydric alcohol such as dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monovalent acid or with a mixture of such acids, such as trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monohydric acid or with a mixture such acids as pentaerythritol tetracaprylate, or a complex ester of monohydric and diacid acids with polyhydric alcohols, eg, a complex ester of trimethylolpropane with caprylic and sebacic acid, or a mixture thereof. In addition to mineral oils such as poly-α-olefins, lubricants based on esters, phosphates, glycols, polyglycols and polyalkylene glycols, and mixtures thereof with water are particularly suitable.

The said lubricants or mixtures thereof may also be treated with an organic. or inorganic. Thickener be added (base fat). Metalworking fluids and hydraulic fluids can be prepared based on the same substances as described above for the lubricants. Often these are also emulsions of such substances in water or other liquids.

Component b) - thiophosphoric acid ester:

R ₁ , R ₂ and R ₃ with the meaning C ₃ -C ₂₀ -hydrocarbon radical are preferably C ₃ -C ₂₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl-C ₁ -C ₄ - alkyl, phenyl, C ₇ -C ₂₀ alkylphenyl, C ₇ -C ₂₀ alkoxyphenyl, naphthyl and C ₇ -C ₉ phenylalkyl.

C ₃ -C ₂₀ -alkyl includes branched or unbranched alkyl radicals. Examples of these are n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, n-heptyl, 3-heptyl , 1-methylhexyl, isoheptyl, n-octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, n-nonyl, 1,1,3-trimethylhexyl, n-decyl, n-undecyl, n Dodecyl, 1-methylundecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl or n-octadecyl. A particularly preferred radical for R ₁ , R ₂ and R ₃ is isopropyl. The meanings of R ₁ , R ₂ and R ₃ may be the same or different. Thiophosphoric acid esters of the formula I are known, for example US Pat. No. 5,531,911.

C ₅ -C ₁₂ -cycloalkyl are, for example, cyclopentyl or -hexyl. C ₅ -C ₁₂ -cycloalkyl-C ₁ -C ₄ -alkyl is, for example, cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl or 2-cyclohexylethyl.

C ₇ -C ₂₀ -alkylphenyl is phenyl which is substituted, for example, by one to three of the above-described C ₁ -C ₄ -alkyl radicals or one to two C ₁ -C ₆ -alkyl radicals or a C ₁ -C ₁₂ -alkyl radical.

C ₇ -C ₂₀ -alkoxyphenyl is phenyl which is substituted, for example, by one to three C ₁ -C ₄ -alkoxy radicals, in particular methoxy or ethoxy, or one to two C ₁ -C ₆ -alkoxy radicals or a C ₁ -C ₁₂ -alkoxy radical is, which are analogous to the aforementioned alkyl radicals.

C ₇ -C ₉ phenylalkyl is, for example, benzyl, 1-phenyl-1-ethyl or 2-phenyl-1-ethyl.

worin x 0 bis 2,7, y 3 - (x + z), z 0 bis 3 - (x + y) und x + y + z = 3 ist, und Ar Phenyl, C₇-C₁₈-Alkylphenyl, C₇-C₁₈-Alkoxyphenyl, Naphthyl und C₇-C₉-Phenylalkyl mit den weiter vorn angegebenen Bedeutungen darstellen. Die Herstellung dieser Thiophosphorsäureester ist in EP-A-368 803 beschrieben. Als Thiophosphorsäureester der Formel sind Triarylthiophosphatgemische vom Typ IRGALUBE 211 mit den Inhaltsstoffen wie n-Decylphenyl-n-nonylphenyl-phenylthiophosphat, o-tert.-Butylphenyl-o-isopropylphenyl- phenylthiophosphat oder n-Hexylphenyl-phenylthiophosphat-Gemische bevorzugt.In a preferred embodiment of the invention, component b) consists of a mixture of thiophosphoric acid esters of the formula:

wherein x is 0 to 2.7, y is 3 - (x + z), z is 0 to 3 - (x + y) and x + y + z is 3, and Ar is phenyl, C ₇ -C ₁₈ alkylphenyl, C ₇ -C ₁₈ alkoxyphenyl, naphthyl and C ₇ -C ₉ phenylalkyl having the meanings given above. The preparation of these thiophosphoric acid esters is described in EP-A-368 803 . As Thiophosphorsäureester the formula Triarylthiophosphatgemische type IRGALUBE 211 with the ingredients such as n-decylphenyl-n-nonylphenyl-phenylthiophosphat, o-tert-butylphenyl-o-isopropylphenyl-phenylthiophosphat or n-hexylphenyl-phenylthiophosphat mixtures are preferred.

In a further preferred embodiment of the invention, component b) consists of a thiophosphoric ester of the triphenylthiophosphate type (IRGALUBE TPPT).

Component c) - dithiophosphoric acid ester or phosphoric acid thioester:

In a compound (II), X is preferably sulfur. R ₁ , R ₂ and R ₃ with the meaning of unsubstituted C ₃ -C ₂₀ -hydrocarbon radicals have the meanings given further below under component b) - thiophosphoric acid esters -, in particular C ₃ -C ₂₀ -alkyl.

worin R_x und R_y Wasserstoff oder C₁-C₄-Alkyl bedeuten, oder das entsprechende Carboxylatsalz. Bevorzugte Bedeutungen von A sind 2-Carboxyeth-1-yl oder 2-C₁-C₄-Alkoxycarbonyleth-1-yl, z.B. Methoxycarbonyleth-1-yl oder Ethoxycarbonylethl -yl, oder Carboxylatsalze davon.In a preferred compound (II) R ₁ and R _{2 are} unsubstituted C ₃ -C ₁₀ -hydrocarbon radicals and R ₃ represents a substituted C ₃ -C ₁₀ -hydrocarbon radical. A substituted C ₃ -C ₁₀ -hydrocarbon radical R ₃ is preferably Carboxy or esterified carboxy-substituted C ₂ -C ₄ -alkyl, for example the partial formula:

wherein R _x and R _{y are} hydrogen or C ₁ -C ₄ alkyl, or the corresponding carboxylate salt. Preferred meanings of A are 2-carboxyeth-1-yl or 2-C ₁ -C ₄ -alkoxycarbonyleth-1-yl, for example methoxycarbonyleth-1-yl or ethoxycarbonylethl-yl, or carboxylate salts thereof.

In a particularly preferred embodiment of the invention, the component b) used is a dithiophosphoric acid ester of the type IRGALUBE 63, which has the structural formula given further, optionally in admixture with a further dithiophosphoric acid ester of the formula II, wherein R ₁ and R _{2 are} isopropyl, isobutyl or 2-ethylhexyl, and R _{3 has} the meaning of the partial formula A, wherein R _x and R _{y are} hydrogen, and 2-carboxy-1-ethyl.

Dithiophosphoric acid esters and phosphoric acid thioesters are known. Their preparation is described, for example, in US Pat. Nos. 4,333,841; 4,544,492 and 3,784,588 and British Patent 1,569,730.

In a preferred embodiment of the invention, the phosphorus content of components b) and c), based on the composition comprising components a), b) and c), is less than 400 ppm. In a particularly preferred embodiment, the phosphorus content of components b) and c) based on the composition comprising components a), b) and c) is 150-390 ppm, in particular 160-370 ppm. The weight ratio of components b) and c) with each other may vary in the ranges of about 10:90 to 95: 5 weight percent.

Component d) - Polyol partial esters, amines and epoxides

By adding a further additive component from the group of Polyolialialester, amines and epoxides, the compositions obtained in contamination better compatibility with water. Suitable oil additives are polyol partial esters, e.g. B. from the group of mono- and diglycerides, monoacetylated or diacetylated monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters and partial fatty acid esters of Polyoxyethylensorbitans. These oil additives are added in a concentration of about 0.01 to 2.0%.

Suitable mono- and diglycerides are derived from glycerol by esterification of one or two hydroxy groups with one or two acid residues of saturated or unsaturated carboxylic acids and even number of 8-20 carbon atoms.

The acid radical of a saturated 8-20 carbon atom saturated carboxylic acid which esterifies the polyglycerol backbone is preferably straight chained with 12, 14, 16 and 18 C atoms, e.g. n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl or n-octadecanoyl.

The acid radical of an even 8-20 carbon atom unsaturated carboxylic acid which esterifies the glycerol backbone is preferably straight chain with 12, 14, 16 and 18 carbon atoms and has 1 double bond, e.g. 9-cis-dodecenoyl, 9-cis-tetradecenoyl, 9-cis-hexadecenoyl or 9-cis-octadecenoyl.

For the acid residues mentioned, the following designations are also common: 9-cis-dodecenoyl (lauroleoyl), 9-cis-tetradecenoyl (myristoleoyl), 9-cis-hexadecenoyl (palmitoleoyl), 6-cis-octadecenoyl (petroseloyl), 6-trans Octadecenoyl (petroselaidoyl), 9-cis-octadecenoyl (Oleoyl), 9-trans-octadecenoyl (elaidoyl), 11-cis-octadecenoyl (vaccenoyl), 9-cis-losenoyl (gadoleoyl), n-dodecanoyl (lauroyl), n-tetradecanoyl (myristoyl), n-hexadecanoyl (palmitoyl ), n-octadecanoyl (stearoyl), n-lcosanoyl (arachidoyl).

Particularly suitable mono- and diglycerides are available under the designations 16 Loxiol ^® G 10 and G (Henkel), Nutrisoft ^® 100 (Grunau), Kessco GMO (Akzo) or Edenor ^® GMO, GDO (Henkel) is commercially available.

A suitable monoacetylated or diacetylated monoglyceride is a monoglyceride which, in addition to the acyl radical of a fatty acid, still preferably has one or even two acetyl radicals. The acyl radical is preferably derived from one of said unsaturated fatty acids having more than ten and an even number of C atoms. Preferred is a monoglyceride which is prepared from a mixture of monoacetylated or diacetylated monoglycerides using the usual separation methods, e.g. fractional distillation, available.

Particularly preferred are acetylated monoglycerides, which are commercially available under the trademark MYVACET (Eastman). Acetylated monoglycerides of the MYVACET series are used industrially as lubricants, plasticizers, nonionic emulsifiers and solubilizers. Particularly preferred are the commercially available under the name MYVACET 5-07, 7-00, 7-07, 9-08, 9-40 and 9-45 K available products.

A suitable polyglycerol fatty acid ester consists of a substantially pure or a mixture of various polyglycerol fatty acid esters wherein the polyglycerol core preferably contains up to and including 10 glycerol units esterified with 1-10 acid residues of said saturated or unsaturated carboxylic acids and even 8-20 carbon atoms.

Suitable polyglycerol fatty acid esters having a uniformly defined structure are, for example, diglycerol monocaprate, diglycerol monolaurate, diglycerol diisostearate, diglycerol monoisostearate, diglycerol tetrastearate (polyglycerol 2-tetrastearate), triglycerol monooleate (polyglyceryl 3-monooleate), triglycerol monolaurate, triglycerol monostearate (US Pat. polyglycerol 3-stearate), triglycerol monoisosterate, hexaglycerol dioleate (polyglycerol 6-dioleate), hexaglycerol distearate (polyglycerol 6-distearate), decaglycerol dioleate (polyglycerol 10-dioleate), decaglycerol tetraoleate (polyglycerol 10-tetraoleate), decaglycerol decaoleate (polyglycerol 10 decaoleate), decaglycerol decastearate (10-decastearate polyglycerol). In brackets the CTFA nomenclature is given. These products are commercially available under the sign Caprol ^® (trademark of. Karlshamns USA Inc., Columbus Ohio). Exact product names: CAPROL 2G4S, 3GO, 3GS, 6G2O, 6G2S, 10G2O, 10G4O, 10G10O, 10G10S. Further products are available under the names DGLC-MC, DGLC-ML, DGLC-DISOS, DGLC-MISOS, TGLC-ML and TGLC-MISOS from Solvay Alkali GmbH, D-3002 Hannover.

Mixtures of different polyglycerol fatty acid esters include names such as decaglycerol mono-, di-oleate, polyglycerol ester of mixed fatty acids, polyglycerol fatty acids, polyglycerol caprate, cocoate, laurate, lanolinate, isostearate or rizinolate and commercially (under the word mark Triodan ^® and HOMODAN ^® Trademark of the company Grindsted Products, Grindsted Denmark), exact product names: TRIODAN 20, 55, R90 and HOMODAN MO, Radiamuls ^® (trademark of the company Petrofina (FINA), Bruxelles Belgium), exact product name RADIAMULS Poly 2253, the name CAPROL PGE860 or ET, or the word sign Plurol ^® (trademark Gattefossé Etablissements, Saint-Priest, France), the exact product PLUROL Stearique WL1009 or WL1173 PLUROL Oleique available. Further products are PGLC-C1010S, PGLC-C0810, PGLC-C1010 / S, PGLC-LT2010, PGLC-LAN0510 / S, PGLC-CT2010 / 90, PGLC-ISOSTUE, PGLC-RUE, PGLC-ISOS0410 Solvay Alkali GmbH, D-3002 Hannover available.

A suitable sorbitan fatty acid ester preferably consists of a substantially pure or a mixture of different sorbitan fatty acid esters in which the sorbitol starting material is esterified with 1-3 acid residues of one of said saturated or unsaturated straight-chain carboxylic acids and even 8-20 carbon atoms.

Suitable sorbitan fatty acid esters are, in particular, sorbitan monolaurate, monopalmitate, monostearate, tristearate, monooleate, sesquioleate and trioleate. These products are commercially available under the mark clamping ^® (trademark of Fa.Atlas, Wilmington USA), specific product names: SPAN 20, 40, 60, 65, 80 and 85, Arlacel ^® (trademark of Fa.Atlas), specific product names: ARLACEL 20, 40, 60, 80, 83, 85 and C, Crill (trademark of Croda Chemicals Ltd, Cowick Hall, Snaith Goole GB.), specific product names: (CRILL 1, and 3 4, Dehymuls ^® trademarks of. Henkel, Dusseldorf DE), specific product names: DEHYMULS SML, SMO, SMS, SSO, Famodan ^® (trademark of Grindsted Products, Grindsted Denmark), specific product. FAMODAN MS and TS, Capmul ^® (trademark of Fa.Karlshamns USA Inc ., Columbus Ohio), specific product names: CAPMULS and O Radiasurf® ^® (trademark of Petrofina (FINA.) Bruxelles Belgium), specific product names: RADIASURF7125, 7135, 7145 and 7155, available.

The said partial fatty acid ester of the polyoxyethylene sorbitan is preferably composed of a substantially pure or mixture of different esters of sorbitan, wherein the structure of the fatty acid groups and the length of the polyoxyethylene chains vary. The sorbitan is preferably etherified by three polyoxyethylene chains and esterified by a fatty acid group. However, the sorbitan can also be etherified by only one or two polyoxyethylene chains and correspondingly esterified by two or three fatty acid groups. Overall, the sorbitol basic body is substituted by at least two and at most four hydrophilic groups, wherein the term "hydrophilic group" summarizes the polyoxyethylene chains and fatty acid groups.

The polyoxyethylene chain is straight-chain and preferably has 4-10, especially 4-8, ethylene oxide units. The ester groups on the sorbitol bulk are derived from a saturated or unsaturated straight chain carboxylic acid of even 8-20 carbon atoms. The ester group derived from this carboxylic acid is preferably straight chained with 12, 14, 16 and 18 C atoms, e.g. n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl or n-octadecanoyl. The ester group derived from an even 8-20 carbon atom unsaturated carboxylic acid is preferably straight chained with 12, 14, 16 and 18 C atoms, e.g. Oleoyl.

Suitable partial of polyoxyethylene sorbitan are available commercially under the trademark Tween ^® from ICI company and the chemical names polyoxyethylene (20 or 4) -sorbitan monolaurate (TWEEN 20 and 21), polyoxyethylene (20) sorbitan monopalmitate or monostearate (TWEEN 40 and 60), polyoxyethylene (4 or 20) sorbitan monostearate or tristearate (TWEEN 61 and 65), polyoxyethylene (20 or 5) sorbitan monooleate (TWEEN 80 or 81) or polyoxyethylene (20) sorbitan trioleate (TWEEN 85) ,

Suitable amines are, for example, primary or secondary amines with the above-described C ₁ -C ₂₀ -alkyl radicals, in particular C ₂ -C ₂₀ -alkyl which may be substituted by hydroxy (alkanolamines) or interrupted by oxygen (etheramines), or polyoxyalkylenediamines, for example or polyoxyalkylenepolyamines, and also primary or secondary amines having C ₅ -C ₆ -cycloalkyl radicals, for example cyclopentyl or cyclohexyl radicals.

Suitable alkanolamines are e.g. Ethanolamine, isopropanolamine, 2-amino-2-methyl-1-propanol, 2- (2-aminoethoxy) ethanol, 3-amino-1-propanol, 2-amino-1-butanol, 2-amino-2-methyl 1,3-propanediol or 2-amino-2-ethyl-1,3-propanediol.

Suitable alkanolamines are commercially available, for example, under the word names Ethomeen and Propomeen (Armak Chemical Division of Akzona, Inc., Chicago USA), eg the products ETHOMEEN C / 15, C / 20, C / 25, O / 12, S / 15 , S / 20, T / 12, T / 15 or T / 25 or the corresponding products of the PROPOMEEN series.

Suitable etheramines are primary etheramines which are commercially available under the word sign Surfam (Mars Chemical Co., Atlanta USA), e.g. the products SURFAM P14B (decyloxypropylamine) or P16A or P17B (tridecyloxypropylamine).

Suitable polyoxyalkylene diamines are, for. B. alkoxylated diamines of the type Ethoduomeen ^® (Armak), eg the products T / 13 and T / 20. Suitable polyoxyalkylenepolyamines are commercially available, for example, under the name JEFFAMINE (Jefferson Chemical Co.), for example the products D-230, D-400, D-1000, D-2000 or T-403.

Suitable epoxides are, for example, C ₄ -C ₂₀ -epoxyalkanes, for example epoxybutane, or esters of C ₁₀ -C ₂₀ -fatty acids, namely esters of epoxidized fatty acids with monohydric alcohols or polyhydric alcohols, for example glycerides. Preference is given to epoxidized esters of fatty acids with monohydric alcohols, for example straight-chain and branched C ₁ -C ₁₀ -alkyl-C ₁ -C ₁₀ -alkoxy, aryl or C ₅ -C ₈ -cycloalkyl esters of C ₁₀ -C ₂₀ -fatty acids, for example Cyclopentyl or cyclohexyl, n-butyl, n-hexyl, benzyl, methoxyethyl, n-octyl, phenyl or tert-butylphenylepoxystearat or oleate and epoxidized soybean oil or linseed oil or epoxidized natural oils and fats, the are known for a high content of unsaturated fatty acids.

Component e) - Ammonium phosphate ester:

In an ammonium phosphate ester of the formula III, R ₁ and R _{2 represent} C ₁ -C ₂₀ -hydrocarbon radicals and R _a , R _b , R _c and R _d independently of one another represent hydrogen or C ₁ -C ₂₀ -hydrocarbon radicals. R ₁ and R ₂ and R _a , R _b , R _c and R _d with the meaning C ₁ -C ₂₀ -hydrocarbon radical are preferably C ₁ -C ₇ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- Butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl or n-heptyl.

In a preferred embodiment, R and R _{2 are} C ₁ -C ₂₀ alkyl, one of R _a , R _b , R _c and R _{d is} hydrogen and the other radicals C ₁ -C ₂₀ alkyl.

The ammonium phosphate ester is added in a low concentration of about 200 to 500 ppm. This addition gives the hydraulic oil particularly good load bearing capacity (FZG fault load levels ≥ 10). In the preferred embodiment, the total phosphorus content of components b), c) and e), based on the total composition, is less than 400 ppm.

Component f) - Oil Additives:

The lubricant compositions mentioned, such as greases, transmission. Metalworking and hydraulic fluids may additionally contain other additives which are added to further enhance their basic properties. These include: antioxidants, metal deactivators, rust inhibitors, viscosity index improvers, pour point depressants, Dispersants, detergents, high pressure additives and antiwear additives. Such additives are added in the amounts customary therefor in the range of from about 0.01 to 10.0% by weight. The following are examples of other additives:

Examples of phenolic antioxidants:

• 1.1. Alkylated monophenols , eg 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butylphenol butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2, 6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxy-methylphenol, linear or side-chain branched nonylphenols such as, for example, 2,6-diol nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl ) -phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.
• 1.2. Alkylthiomethylphenols, eg 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4 -nonylphenol.
• 1.3. Hydroquinones and alkylated hydroquinones , eg 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl- 4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di- tert-butyl-4-hydroxyphenyl-stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
• 1.4. Tocopherols , for example α-, β-, γ- or δ- and mixtures thereof (vitamin E).
• 1.5. Hydroxylated thiodiphenyl ethers , for example 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6-tert -butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec-amylphenol), 4,4'-bis (dimethyl-2,6-4-hydroxyphenyl) disulfide.
• 1.6. Alkylidene bisphenols , eg 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-bis Methylenebis [4-methyl-6- (a-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl) 4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'- Ethylidene bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6- (a , α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol) 1,1-Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1 , 1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -dicyclopentadiene, Bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-bis) dimethyl-2-hydroxyphenyl) -butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -propane, 2,2-bis (5-tert-butyl-4-hydroxy-2- methylphenyl) -4-n-dodecylmercapto-butane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane.
• 1.7. O-, N- and S-benzyl compounds , eg 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4-tert-butyl-3-hydroxy-2,6 -dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
• 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis malonate (3,5-di-tert-butyl-2-hydroxybenzyl) dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethylbutyl) -phenyl] - 2,2-bis malonate (3,5-di-tert-butyl-4-hydroxybenzyl).
• 1.9. Hydroxybenzyl aromatics , eg, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -phenol.
• 1.10. Triazine compounds , for example 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5 -di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5 triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-diisobutyl) tert -butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
• 11.1. Acylaminophenols , eg 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester.
• 1.12. Esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol , 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3 Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• 1.13. Esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as, for example, with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol , 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3 Thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• 1.14. Esters of beta- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl 1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• 1.15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2 Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 - phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• 16.1. Amides of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid , such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine.
• 1.17. Ascorbic acid (vitamin C).
• 1.18. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p phenylenediamine, N, N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl- p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di- (naphthyl-2) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluene-sulfonamido) -diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1 naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, eg, p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4 Nonanoylamino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylaminophenol, di- (4-methoxyphenyl) -amine, 2,6-di-tert-bu tyl-4-dimethylamino-methylphenol, 2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1 , 2-Di - [(2-methyl-phenyl) -amino] -ethane, 1,2-di- (phenylamino) -propane, (o-tolyl) -biguanide, di- [4- (1 ', 3' -dimethyl-butyl) -phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-Octyldiphenylaminen, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated Dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated and dialkylated tert-butyl / tert-octyl-phenothiazines, mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidin-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6 , 6-tetramethypiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

Examples of other antioxidants:

Aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11-trithiatridecan and 2,2,15,15 tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecan.

Examples of metal deactivators, e.g. for copper:

1. a) Benzotriazoles and their derivatives, e.g. 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4- or 5-alkylbenzotriazoles (e.g., tolutriazole) and their derivatives, 4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylene-bis-benzotriazole; Mannich bases of benzotriazole or tolutriazole such as 1- [di (2-ethylhexyl) aminomethyl)] tolutriazole and 1- [di (2-ethylhexyl) aminomethyl)] benzotriazole; Alkoxyalkylbenzotriazoles such as 1- (nonyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl) tolutriazole.
2. b) 1,2,4-triazoles and their derivatives, e.g. 3-alkyl (or aryl) -1,2,4-triazoles, Mannich bases of 1,2,4-triazoles such as 1- [di (2-ethylhexyl) aminomethyl-1,2,4-triazole; Alkoxyalkyl-1,2,4-triazoles such as 1- (1-butoxyethyl) -1,2,4-triazole; acylated 3-amino-1,2,4-triazoles.
3. c) imidazole derivatives, e.g. 4,4'-methylenebis (2-undecyl-5-methylimidazole), bis [(N-methyl) -imidazol-2-yl] carbinol octyl ether.
4. d) Sulfur-containing heterocyclic compounds, e.g. 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and their derivatives; 3,5-Bis [di- (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one.
5. e) amino compounds, e.g. Salicylidene-propylenediamine, salicylaminoguanidine and their salts.

Examples of rust inhibitors:

1. a) organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl and alkenylsuccinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, Alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, dodecyloxy (ethoxy) -acetic acid and its amine salts, furthermore N-oleoyl-sarcosine, sorbitan-mono-oleate, lead naphthenate, alkenylsuccinic anhydrides, eg dodecenylsuccinic anhydride, 2- (2-carboxyethyl) -1 dodecyl-3-methylglycerol and its salts, in particular sodium and triethanolamine salts.
2. b) Nitrogen-containing compounds, eg:
   1. i. Tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates, furthermore 1- [N, N-bis (2-hydroxyethyl) amino] -3- (4-nonylphenoxy) propan-2-ol.
   2. ii. Heterocyclic compounds, for example: Substituted imidazolines and oxazolines, for example 2-heptadecenyl-1- (2-hydroxyethyl) -imidazoline
3. c) Sulfur-containing compounds, for example barium-dinonylnaphthalenesulfonates, calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and their salts.

Examples of viscosity index improvers: polyacrylates, polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.

Examples of pour point depressants: poly (meth) acrylates, ethylene-vinyl acetate copolymer, alkyl polystyrenes, fumarate copolymers, alkylated naphthalene derivatives.

Examples of dispersants / surfactants : polybutenylsuccinic amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulphonates and phenolates.

Examples of high pressure and wear protection additives:

Sulfur and halogen containing compounds such as e.g. chlorinated paraffins, sulfurized olefins or vegetable oils (soybean oil, rapeseed oil), alkyl or aryl di- or trisulfides, benzotriazoles or derivatives thereof such as bis (2-ethylhexyl) aminomethyl tolutriazole, dithiocarbamates such as methylene-bis-dibutyldithiocarbamate, derivatives of 2-Mercaptobenzothiazoles such as 1- [N, N-bis (2-ethylhexyl) aminomethyl] -2-mercapto-1H-1,3-benzothiazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole such as 2 , 5-bis (tert.nonyldithio) -1,3,4-thiadiazole.

Examples of Reibwertverminderer , for example, oil from lard, oleic acid, tallow, rapeseed oil, sulfurized fats, amines. Further examples are mentioned in EP 565487.

• Emulgatoren: Petroleumsulfonate, Amine wie polyoxyethylierte Fettamine, nichtionische oberflächenaktive Substanzen; Puffer: Alkanolamine; Biocide: Triazine, Thiazolinone, Tris-Nitromethan, Morpholin, Natriumpyridenethiol; Verarbeitungsgeschwindigkeitsverbesserer: Calcium- und Bariumsulfonate;

Examples of particular additives for use in water / oil-metalworking and hydraulic fluids are:

• Emulsifiers : petroleum sulfonates, amines such as polyoxyethylated fatty amines, nonionic surfactants; Buffer: alkanolamines; Biocides: triazines, thiazolinones, tris-nitromethane, morpholine, sodium pyridethiol ; Processing speed improvers: calcium and barium sulfonates;

The components mentioned can be admixed to the lubricants in a manner known per se. It is also possible to produce a concentrate or a so-called additive package, which can be diluted in accordance with consumption to use concentrations for the corresponding lubricant.

1. a) ein Grundöl mit schmierender Viskosität, welches man für Fette, Metallbearbeitungs-, Getriebe- und Hydraulikflüssigkeiten verwendet;
2. b) mindestens einen Thiophosphorsäureester aus der Gruppe der Thiophosphorsäureester der Formel I, worin R₁, R₂ und R₃ Phenyl bedeuten, oder Gemische von Thiophosphorsäureestern der Formel I', worin x 0 bis 2,7, y 3 - (x + z), z 0 bis 3 - (x + y) und x + y + z = 3 ist, und Ar Phenyl oder C₇-C₁₈-Alkylphenyl darstellen;
3. c) mindestens einen Dithiophosphorsäureester der Formel II, worin X Schwefel, R₁ und R₂ C₃-C₁₀-Alkyl und R₃ 2-Carboxyeth-1-yl oder 2-C₁-C₄-Alkoxycarbonyleth-1-yl bedeuten, oder Salze davon;
4. d) mindestens ein Öladditiv aus der Gruppe der Polyolpartialester, Amine und Epoxide, welche dadurch gekennzeichnet ist, dass der Phosphorgehalt der Thiophosphorsäureester-Komponente b), kombiniert mit der Dithiophosphorsäureester- oder Phosphorsäurethioester-Komponente c), bezogen auf die Zusammensetzung mit den Komponenten a), b) und c) weniger als 400 ppm beträgt.

A preferred embodiment of the invention relates to a composition comprising

1. a) a lubricating viscosity base oil which is used for greases, metalworking, gear and hydraulic fluids;
2. b) at least one thiophosphoric acid ester from the group of thiophosphoric acid esters of the formula I in which R ₁ , R ₂ and R _{3 are} phenyl, or mixtures of thiophosphoric acid esters of the formula I ', wherein x is 0 to 2,7, y 3 - (x + z ), z is 0 to 3 - (x + y) and x + y + z = 3, and Ar is phenyl or C ₇ -C ₁₈ alkylphenyl;
3. c) at least one dithiophosphoric acid ester of the formula II in which X is sulfur, R ₁ and R _{2 are} C ₃ -C ₁₀ -alkyl and R _{3 is} 2-carboxyeth-1-yl or 2-C ₁ -C ₄ -alkoxycarbonyleth-1-yl , or salts thereof;
4. d) at least one oil additive from the group of Polyolialialester, amines and epoxides, which is characterized in that the phosphorus content of the thiophosphoric ester component b), combined with the Dithiophosphorsäureester- or Phosphorsäurethioester component c), based on the composition with the components a ), b) and c) is less than 400 ppm.

1. a) ein Grundöl mit schmierender Viskosität, welches man für Fette, Metallbearbeitungs-, Getriebe- und Hydraulikflüssigkeiten verwendet;
2. b) mindestens einen Thiophosphorsäureester aus der Gruppe der Thiophosphorsäureester der Formel I, worin R₁, R₂ und R₃ Phenyl bedeuten, oder Gemische von Thiophosphorsäureestern der Formel I', worin x 0 bis 2,7, y 3 - (x + z), z 0 bis 3 - (x + y) und x + y + z = 3 ist, und Ar Phenyl oder C₇-C₁₈-Alkylphenyl darstellen;
3. c) mindestens einen Dithiophosphorsäureester der Formel II, worin X Schwefel, R₁ und R₂ C₃-C₁₀-Alkyl und R₃ 2-Carboxyeth-1-yl oder 2-C₁-C₄-Alkoxycarbonyleth-1-yl bedeuten, oder Salze davon,
4. d) mindestens ein Öladditiv aus der Gruppe der Polyolpartialester, Amine und Epoxide; und
5. e) mindestens ein Ammoniumphosphatester der Formel III, worin R₁ und R₂ C₁-C₂₀-Alkyl, einer der Reste R_a, R_b, R_c und R_d Wasserstoff und die anderen Reste C₁-C₂₀-Alkyl darstellen; und
6. f) übliche Öladditive, welche dadurch gekennzeichnet ist, dass der Phosphorgehalt der Komponenten b), c) und e), bezogen auf die Gesamtzusammensetzung, weniger als 400 ppm beträgt.

Another particularly preferred embodiment of the invention relates to a composition comprising

1. a) a lubricating viscosity base oil which is used for greases, metalworking, gear and hydraulic fluids;
2. b) at least one thiophosphoric acid ester from the group of thiophosphoric acid esters of the formula I in which R ₁ , R ₂ and R _{3 are} phenyl, or mixtures of thiophosphoric acid esters of the formula I ', wherein x is 0 to 2,7, y 3 - (x + z ), z is 0 to 3 - (x + y) and x + y + z = 3, and Ar is phenyl or C ₇ -C ₁₈ alkylphenyl;
3. c) at least one dithiophosphoric acid ester of the formula II in which X is sulfur, R ₁ and R _{2 are} C ₃ -C ₁₀ -alkyl and R _{3 is} 2-carboxyeth-1-yl or 2-C ₁ -C ₄ -alkoxycarbonyleth-1-yl , or salts thereof,
4. d) at least one oil additive from the group of polyol partial esters, amines and epoxides; and
5. e) at least one ammonium phosphate ester of the formula III in which R ₁ and R _{2 are} C ₁ -C ₂₀ -alkyl, one of the radicals R _a , R _b , R _c and R _{d is} hydrogen and the other radicals C ₁ -C ₂₀ -alkyl ; and
6. f) customary oil additives, which is characterized in that the phosphorus content of components b), c) and e), based on the total composition, is less than 400 ppm.

• b) mindestens einen Thiophosphorsäureester der Formel:
  
  worin R₁, R₂ und R₃ C₃-C₂₀-Kohlenwasserstoffreste darstellen; und
• c) mindestens einen Dithiophosphorsäureester oder Phosphorsäurethioester der Formel:
  
  worin X Sauerstoff oder Schwefel und R₁, R₂ und R₃ unsubstituierte oder substituierte C₃-C₂₀-Kohlenwasserstoffreste darstellen; und
• d) mindestens ein Öladditiv aus der Gruppe umfassend Polyolpartialester, Alkanolamine, Etheramine, primäre oder sekundäre Amine mit C₁-C₂₀Alkylresten, primäre oder sekundäre Amine mit C₂-C₂₀Alkylresten, die durch Hydroxy substituiert oder Sauerstoff unterbrochen sind, Polyoxyalkylendiamine, Polyoxyalkylenpolyamine, primäre oder sekundäre Amine mit C₅-C₆Cycloalkylresten und Epoxide.

The invention likewise provides a concentrate which can be used for the preparation of the composition

• b) at least one thiophosphoric acid ester of the formula:
  
  wherein R ₁ , R ₂ and R _{3 represent} C ₃ -C ₂₀ hydrocarbon radicals; and
• c) at least one dithiophosphoric acid ester or phosphoric acid thioester of the formula:
  
  wherein X represents oxygen or sulfur and R ₁ , R ₂ and R _{3 represent} unsubstituted or substituted C ₃ -C ₂₀ hydrocarbon radicals; and
• d) at least one oil additive from the group comprising polyol partial esters, alkanolamines, ether amines, primary or secondary amines having C ₁ -C ₂₀ -alkyl radicals, primary or secondary amines having C ₂ -C ₂₀ -alkyl radicals which are substituted by hydroxy or interrupted by oxygen, polyoxyalkylenediamines, Polyoxyalkylenepolyamines, primary or secondary amines with C ₅ -C ₆ cycloalkyl radicals and epoxides.

• e) ein Ammoniumphosphatester der Formel:
  
  worin R, und R₂ C₁-C₂₀-Kohlenwasserstoffreste und R_a, R_b, R_c und R_d unabhängig voneinander Wasserstoff oder C₁-C₂₀-Kohlenwasserstoffreste darstellen ; und
• f) übliche Öladditive.

The concentrate may contain the following additional ingredients:

• e) an ammonium phosphate ester of the formula:
  
  wherein R, and R _{2 are} C ₁ -C ₂₀ hydrocarbon radicals and R _a , R _b , R _c and R _{d are} independently hydrogen or C ₁ -C ₂₀ hydrocarbon radicals; and
• f) usual oil additives.

The components are so assembled in the concentrate that it is liquid at room temperature without the addition of the base oil a) or a solvent.

The invention also relates to a process for improving the service properties of lubricants, characterized by adding components b), c) and d) preferably in a concentration such that the phosphorus content of these components, based on the total composition, is less than 400 ppm.

Likewise provided by the invention is the use of compounds of components b) c) and d), preferably in said concentration, as additives in engine oils, turbine oils, gear oils, hydraulic fluids, metalworking fluids or lubricating greases.

The following examples illustrate the invention:

Examples 1-15 and Reference Examples (Prior Art I and II)

The various blends were prepared using ISO VG 46 mineral oil (kinematic viscosity at 40 ° C: 42-50 CSt) and a base-additive mixture typically used for hydraulic fluids. This base additive blend is free of metal salts and is used at 0.29-0.47% (wt%). It is a combination of an aromatic amine antioxidant (such as Irganox ^® L 57), a hindered phenol antioxidant (such as Irganox ^® L 135) and smaller amounts of other conventional additives such as pour point depressants (eg: Plexol ^® 154), anti-foaming agents (eg, Mobilad C402 ^®), Demulgieradditive (eg Synperonic ^® PEL81), corrosion inhibitors (for example, Irgacor ^® NPA) and metal (such as Irgamet ^® 39). The additives and mixtures used as well as the results of the tests carried out are listed in the table. Formulations 9, 10, 11, 12, 13, 14 correspond to the claimed composition of the present invention. The other formulations serve for comparison, in particular with the prior art (states of Tables I and II).

The following tests were carried out: Testing of: anti-wear properties: VKA and

1. 1. VKA (Vierkugelapparat von Shell gemäss DIN 51530, IP 239) - Bestimmung der Verschteisskennwerte (engl. wear scar diameter (WSD) flüssiger Schmierstoffe gemäss DIN 51350 T3; U/min: 1420, Last: 40 kg (400 N), Dauer: 1 Std (h); Gute Werte: < 0,45 mm
2. 2. SRV (Schwing-Reib-Verschleissgerät der Fa. Optimol Instruments, DE-München) gemäss DIN 51834 (im Gelbdruck); Messung des Verschleisses an der Platte; Prinzip: Eine Stahlkugel, auf die eine vertikale Kraft FN wirkt, führt auf einem fixen Stahlzylinder eine oszillierende Gleitbewegung aus; System: Kugel/Platte; Last: 300 N, Dauer: 2 h, Temperatur: 100°C, Frequenz: 50 Hz (Als Temperatur wurde abweichend zur DIN 51834 T2 100°C statt 50°C gewählt, da für die eingangs erwähnte Spezifikation der Fa. Denison Hydraulics (HFO) eine Temperatur von 100°C für den notwendigen P 46 Kolbenpumpentest gefordert wird). Gemessen wurde der Verschleiss auf der Platte. Hierbei wurde mit einem Talysurf-Gerät die Oberfläche der Platte mit der Verschleisskalotte abgetastet und die grösste Vertiefung gemessen. Der Abstand der grössten Vertiefung zur Plattenoberfläche wird in µm Profiltiefe als Verschleissmerkmal angegeben. Bei den angegebenen Verschleisswerten handelt es sich um relative Verschleisswerte. Hohe Werte (> 3 µm) bedeuten hohen Verschleiss.
3. 3. Der Test Kompatibilität mit Wasser dient der Prüfung des Einflusses von Wasser auf zwei wichtige Eigenschaften eines Hydauliköls: Filtrierbarkeit und Rostschutz. 1,5 1 der zu prüfenden Flüssigkeit werden zuerst zusammen mit 1% Wasser 10 Tage bei 100°C gealtert (geschlossenes Gefäss), wobei jeden Tag das Gefäss 1 Min. stark geschüttelt wird. Nach 10 Tagen werden 3 x 300 ml der gealterten Flüssigkeit entsprechend den Bedingungen des Standard AFNOR Filtrationstests E-48-691 oder E-48 690 an 0,8 µm Filter mit Druck (1 bar) filtriert. Das Ergebnis dieses Tests wird als Filtrationsindex Fl angegeben und stellt den Durchschnitt aus 3 Einzelmessungen dar. Fl = T₃₀₀-T₂₀₀/2(T₁₀₀-T₅₀); T₃₀₀ = Zeit in Sekunden, wenn 300 ml den Filter passiert haben; T₂₀₀ = Zeit in Sekunden, wenn 200 ml den Filter passiert haben, und so weiter. Werte < 2 gelten als "Pass", Werte > 2 als "fail"(gemäss Spezifikation: Denison HF 0). Weiterhin werden die restlichen 600 ml der gealterten und mit 1% Wasser kontaminierten Flüssigkeit einem Rosttest (Doppelversuch je 300 ml) nach dem Standart ASTM D 665 B unterzogen. Hierbei wird ein rostfrei geschliffener Stahlbolzen für 24h bei 60° in der Mischung aus 300 ml (schon mit 1% dest. Wasser kontaminierten) Testöl und 30 ml Seewasser gehalten, die mit einem Rührer stark umgewälzt wird. Nach Herausnehmen des Stahlbolzen wird visuell der Korrosionsgrad beurteilt. Bewertung 0 = keine Korrosion, Bewertung 3 = starke Korrosion.
4. 4. FZG-Getriebetest (Beschreibung in DIN 51.354, A/8.3/90, IP 334/79). Im Tauchschmierverfahren laufen in der zu prüfenden Flüssigkeit definierte Zahnräder bei konstanter Drehzahl und festgelegter Anfangstemperatur. Die Belastung der Zahnräder wird stufenweise gesteigert. Ab Kraftstufe 4 wird nach jeder Kraftstufe die Veränderung der Zahnflanken durch Beschreibung und gegebenenfalls Photo, Rauheitsmessung oder Kontaktabdruck festgehalten. Die Grenzlaststufe liegt eine Stufe unter der sogenannten Fehlerlaststufe (kurz: FLS), bei der mindestens zwei Flanken des Prüfzahnrades eindeutige Schäden (Risse oder ähnliches) aufweisen.

Tabelle 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Stand d.T.I Stand. d.T.II Komponente b)₁ ¹ 0,50 0,35 0,10 0,10 0,25 0,25 Komponente b)₂ ² 0,56 0,37 0,15 0,15 0,15 0,15 0,050 Komponente c)₁ ³ 0,225 0,36 0,25 0,225 0,225 0,27 0,27 0,23 0,12 0,30 0,30 Komponente c)₂ ⁴ 0,4 Komponente d)₁ ⁵ 0,025 0,025 0,03 0,03 0,025 0,013 Komponente d)₂ ⁶ 0,08 0,08 0,08 0,04 Komponente d)₃ ⁷ 0,025 Komponente e)⁸ 0,03 0,03 0,03 0,035 Ammoniumsultonat⁹(Nasul®TA) 0,05 Phosphorgehalt¹⁰ von b) und c) bezogen auf die Zusammensetzung mit den Komponenten a),b) und c) (ppm) 0 455 319 437 289 232 371 376 373 349 349 369 369 354 163 537 537 VKA (DIN 51 530, IP 239) -- Wear scar diameter 60 min, 400 N, 40°C, 1400 U/min [mm] 0,62 0,9 0,9 0,43 0,59 0,43 - 0,42 - 0,42 0,40 0,41 - 0,38 0,44 0,41 - SRV - Kugel/Platte System (300 N, 2 h, 100°C, 50 Hz) - Kalottenverschleiss    Platte -max. Profiltiefe    [µm] 8,0 12,0 - 7,0 - 8,7 0,9 1,4 - 0,9 - 0,7 - 0,8 0,9 0,5 - Spezieller Wasserkompatiblitätstest Lsg. Öl+1% dest. H₂O gelagert bei trübe 100°C/10 Tage, danach: bei - AFNOR-Druck-Filtration RT an 0.8 µm Filter FI - Stahl-Korrosionstest 1,1 1,2 - 1,3 - 1,4 1,5 1,6 1,3 1,2 1,1 1,1 1,2 1,1 1,2 1,35 1,3¹¹ ASTM D 665 B 0 0 - 0 - 1 2 2 1 0,5 0 0 0 0 0 3 2 FZG/FLS (DIN 51 354.17/8.3/90) 7 - 7 - 8 8 8 - 8 - 12 - 12 11 10 - ¹ Komponente b)₁: Irgalube^® TPPT (Triphenylthionophosphat)
² Komponente b)₂: flüssiges Gemisch von Tri[(alkyl)aryl]thionophosphaten wie in EP 368803 beschrieben
³ Komponente c)₁: Irgalube^® 63 {3-[(Bis-isopropyloxy-phosphinothioyl)-thio]-propionsäure-ethylester}
⁴ Komponente c)₂: Bis(O,O-Dialkyldithiophosphat)
⁵ Komponente d)₁: Epoxidiertes-Isooctylstearat (z.B.: Edenol^® B33 ex Henkel)
⁶ Komponente d)₂: Glycerin-monooleat (z.B..: Kessco* GMO ex Akzo)
⁷ Komponente d)₃: Oleylamin (z.B.: Armeen* O, OD ex Akzo)
⁸ Komponente e): Irgalube* 349 (Ammoniumphosphatester)
⁹ Diethylentretaammoniumdinonylnaphtylsultonat (NA-SUL^{® DTA ex KING)
10} kalkuliert auf Basis der Summenformel
¹¹Grober Niederschlag auf Filterpapier SRV, compatibility with water (special storage of the oil with water, then filtration and rust test), load bearing capacity (extreme pressure): FZG.

1. 1. VKA (four-ball apparatus from Shell according to DIN 51530, IP 239) - Determination of wear scar diameter (WSD) of liquid lubricants in accordance with DIN 51350 T3, rpm: 1420, load: 40 kg (400 N), duration : 1 hr (h) Good values: <0.45 mm
2. 2. SRV (vibratory friction wear device from the company Optimol Instruments, DE-Munich) according to DIN 51834 (in yellow pressure); Measuring the wear on the plate; Principle: A steel ball, on which a vertical force FN acts, executes an oscillating sliding movement on a fixed steel cylinder; System: ball / plate; Load: 300 N, duration: 2 h, temperature: 100 ° C, frequency: 50 Hz (In contrast to DIN 51834 T2, the temperature was chosen to be 100 ° C instead of 50 ° C, as for the specification of Fa. Denison Hydraulics (HFO) a temperature of 100 ° C is required for the necessary P 46 piston pump test). The wear on the plate was measured. In this case, the surface of the plate with the wear dome was scanned with a Talysurf device and the largest depression was measured. The distance of the largest depression to the plate surface is given in μm profile depth as a wear feature. The specified wear values are relative wear values. High values (> 3 μm) mean high wear.
3. 3. The water compatibility test is used to test the influence of water on two important properties of a hydaulic oil: filterability and rust prevention. 1.5 l of the liquid to be tested are first aged together with 1% water for 10 days at 100 ° C. (closed vessel), the vessel being shaken vigorously for 1 min each day. After 10 days, 3 x 300 ml of the aged liquid are filtered under pressure according to the conditions of the standard AFNOR filtration test E-48-691 or E-48 690 to 0.8 μm filter with pressure (1 bar). The result of this test is given as filtration Fl Index and represents the average of 3 individual measurements Fl = T ₃₀₀ T _200/2 (T ₁₀₀ -T _50). T ₃₀₀ = time in seconds when 300 ml have passed the filter; T ₂₀₀ = time in seconds when 200 ml have passed the filter, and so on. Values <2 are considered "pass", values> 2 as "fail" (according to specification: Denison HF 0). Furthermore, the remaining 600 ml of the aged and contaminated with 1% water liquid a rust test (double test per 300 ml) according to the standard ASTM D 665 B subjected. In this case, a stainless-ground steel stud is kept for 24 h at 60 ° in the mixture of 300 ml (already contaminated with 1% of water) test oil and 30 ml of seawater, which is strongly circulated with a stirrer. After removing the steel bolt, the degree of corrosion is assessed visually. Rating 0 = no corrosion, rating 3 = severe corrosion.
4. 4. FZG gearbox test (description in DIN 51.354, A / 8.3 / 90, IP 334/79). In the immersion lubrication process, defined gears run in the liquid to be tested at a constant speed and a fixed starting temperature. The load on the gears is gradually increased. From force level 4, the change in the tooth flanks is recorded by description and, if necessary, photo, roughness measurement or contact print after each power stage. The limit load stage is one stage below the so-called fault load level (FLS for short), in which at least two flanks of the test gear have clear damage (cracks or the like).

table 1 2 3 4 5 6 7 8th 9 10 11 12 13 14 15 Stand dTI Stand. DTII Component b) ₁ ¹ 0.50 0.35 0.10 0.10 0.25 0.25 Component b) ₂ ² 0.56 0.37 0.15 0.15 0.15 0.15 0,050 Component c) ₁ ³ 0.225 0.36 0.25 0.225 0.225 0.27 0.27 0.23 0.12 0.30 0.30 Component c) ₂ ⁴ 0.4 Component d) ₁ ⁵ 0,025 0,025 0.03 0.03 0,025 0,013 Component d) ₂ ⁶ 0.08 0.08 0.08 0.04 Component d) ₃ ⁷ 0,025 Component e) ⁸ 0.03 0.03 0.03 0,035 Ammonium sultonate ⁹ (Nasul®TA) 0.05 Phosphorus content ¹⁰ of b) and c) related to the Composition with the Components a), b) and c) (Ppm) 0 455 319 437 289 232 371 376 373 349 349 369 369 354 163 537 537 VKA (DIN 51 530, IP 239) - Wear scar diameter 60 minutes, 400 N, 40 ° C, 1400 rpm [mm] 0.62 0.9 0.9 0.43 0.59 0.43 - 0.42 - 0.42 0.40 0.41 - 0.38 0.44 0.41 - SRV - ball / plate system (300 N, 2 h, 100 ° C, 50 Hz) - calotte wear plate -Max. Tread depth [μm] 8.0 12.0 - 7.0 - 8.7 0.9 1.4 - 0.9 - 0.7 - 0.8 0.9 0.5 - Special water compatibility test Sol. Oil + 1% dist. H ₂ O stored at cloudy 100 ° C / 10 days, then: at - AFNOR pressure filtration RT at 0.8 μm filter FI - Steel corrosion test 1.1 1.2 - 1.3 - 1.4 1.5 1.6 1.3 1.2 1.1 1.1 1.2 1.1 1.2 1.35 1.3 ¹¹ ASTM D 665 B 0 0 - 0 - 1 2 2 1 0.5 0 0 0 0 0 3 2 FZG / FLS (DIN 51 354.17 / 8.3 / 90) 7 - 7 - 8th 8th 8th - 8th - 12 - 12 11 10 - ¹ component b) is _1: Irgalube TPPT ^® (Triphenylthionophosphat)
² Component b) ₂ : liquid mixture of tri [(alkyl) aryl] thionophosphates as described in EP 368803
³ Component c) is _1: Irgalube ^® 63 {3 - [(Bis-isopropyloxy-phosphinothioyl) thio] -propionate}
⁴ component c) ₂ : bis (O, O-dialkyldithiophosphate)
⁵ component d) is _1: Epoxidized-isooctyl (eg Edenol B33 ^® ex Henkel)
⁶ component d) ₂ : glycerol monooleate (for example: Kessco * GMO ex Akzo)
⁷ Component d) ₃ : Oleylamine (eg: Armeen * O, OD ex Akzo)
⁸ component e): Irgalube * 349 (ammonium phosphate ester)
⁹ Diethylenetretaammonium dinonylnaphthylsultonate (NA-SUL® ^{DTA ex KING)
10} calculated on the basis of the empirical formula
¹¹ Coarse precipitate on filter paper

Claims (10)

1. A composition comprising:

   a) a base oil of lubricating viscosity;

   b) at least one thiophosphoric acid ester of formula:

   

   wherein R₁, R₂ and R₃ are C₃-C₂₀hydrocarbon radicals;

   c) at least one dithiophosphoric acid ester or phosphoric acid thioester of formula:

   

   wherein X is oxygen or sulfur and R₁, R₂ and R₃ are unsubstituted or substituted C₃-C₂₀hydrocarbon radicals; and

   d) at least one oil additive from the group of the polyol partial esters, alkanolamines, ether amines, primary or secondary amines with C₁-C₂₀alkyl radicals, primary or secondary amines with C₂-C₂₀alkyl radicals substituted by hydroxy or interrupted by oxygen, polyoxyalkylenediamines, polyoxyalkylenepolyamines, primary or secondary amines with C₅-C₆cycloalkyl radicals and epoxides.
2. A composition according to claim 1, wherein the phosphorus content of the thiophosphoric acid ester component b) combined with the dithiophosphoric acid ester or phosphoric acid thioester component c), based on the composition comprising components a), b) and c), is less than 400 ppm.
3. A composition according to claim 1 comprising b) at least one thiophosphoric acid ester of formula I wherein R₁, R₂ and R₃ are substituents from the group C₃-C₂₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₂bicycloalkyl, phenyl, C₇-C₁₈alkylphenyl, C₇-C₁₈alkoxyphenyl, naphthyl and C₇-C₉phenylalkyl.
4. A composition according to claim 1 comprising b) a mixture of thiophosphoric acid esters of formula:

   

   wherein x is from 0 to 2.7, y is 3 - (x + z), z is from 0 to 3 - (x + y) and x + y + z = 3, and Ar is phenyl, C₇-C₁₈alkylpheny, C₇-C₁₈alkoxyphenyl, naphthyl or C₇-C₉phenylalkyl.
5. A composition according to claim 1 comprising c) at least one dithiophosphoric acid ester of formula II wherein X is sulfur, R₁ and R₂ are C₃-C₁₀alkyl and R₃ is C₂-C₄alkyl substituted by carboxy or esterified carboxy, or a salt thereof.
6. A composition according to claim 1 comprising c) at least one dithiophosphoric acid ester of formula II wherein X is sulfur, R₁ and R₂ are C₃-C₁₀alkyl and R₃ is 2-carboxyeth-1-yl or 2-C₁-C₄alkoxycarbonyleth-1-yl, or a salt thereof.
7. A composition according to claim 1 comprising

   a) a base oil of lubricating viscosity used for greases, for metal-working fluids, for gear fluids or for hydraulic fluids;

   b) at least one thiophosphoric acid ester from the group of the thiophosphoric acid esters of formula I wherein R₁, R₂ and R₃ are phenyl, or mixtures of thiophosphoric acid esters of formula I' wherein x is from 0 to 2.7, y is 3 - (x + z), z is from 0 to 3 - (x + y) and x + y + z = 3, and Ar is phenyl or C₇-C₁₈alkylphenyl;

   c) at least one dithiophosphoric acid ester of formula II wherein X is sulfur, R₁ and R₂ are C₃-C₁₀alkyl and R₃ is 2-carboxyeth-1-yl or 2-C₁-C₄alkoxycarbonyleth-1-yl, or a salt thereof,

   d) at least one oil additive from the group of the polyol partial esters, amines and epoxides, characterized in that the phosphorus content of the thiophosphoric acid ester component b) combined with the dithiophosphoric acid ester or phosphoric acid thioester component c), based on the composition comprising components a), b) and c), is less than 400 ppm.
8. A concentrate comprising

   b) at least one thiophosphoric acid ester of formula:

   

   wherein R₁, R₂ and R₃ are C₃-C₂₀hydrocarbon radicals; and

   c) at least one dithiophosphoric acid ester or phosphoric acid thioester of formula:

   

   wherein X is oxygen or sulfur and R₁, R₂ and R₃ are unsubstituted or substituted C₃-C₂₀hydrocarbon radicals; and

   d) at least one oil additive from the group of polyol partial esters, alkanolamines, ether amines, primary or secondary amines with C₁-C₂₀alkyl radicals, primary or secondary amines with C₂-C₂₀alkyl radicals substituted by hydroxy or interrupted by oxygen, polyoxyalkylenediamines, polyoxyalkylenepolyamines, primary or secondary amines with C₅-C₆cycloalkyl radicals and epoxides.
9. A method of improving the performance properties of a lubricant, which comprises adding to the lubricant at least one composition according to claim 1.
10. The use of a composition according to claim 1 in improving the performance properties of lubricants.