BR112012032500B1 - lubricating compositions for vehicle engine transmissions - Google Patents

Abstract

The invention relates to a lubricating composition comprising: (a) an organomolybdenum compound, (b) one or more extreme pressure and anti-wear additives chosen from thia (di) azois, (c) one or more phosphorus-containing additives or containing anti-wear and extreme pressure phosphorus-sulfur chosen from phosphites, phosphates, phosphonates, thiophosphates or thiophosphites, said lubricant composition having a molybdenum weight content between 90 and 350 ppm. use for gearbox lubrication.

Description

LUBRICANT COMPOSITIONS FOR VEHICLE ENGINE TRANSMISSIONS

TECHNICAL FIELD

The present invention relates to lubricating compositions, in particular to automotive transmissions, particularly lubricating compositions for manual gearboxes.

TECHNOLOGICAL HISTORY

Automotive vehicle transmission components operate under a high load and at high speeds. The oils for these transmissions must therefore be particularly protective of the parts against wear and fatigue, and notably protect the gear teeth against flaking.

The peeling occurs after a long period of time, preceding visible deteriorations. The mechanisms are not well known, but the phenomenon begins with the initiation of cracks and a certain depth below the surface, these cracks propagate and when normal cracks are generated on the surface, chips are suddenly released.

The prevention of this phenomenon requires a reduction in contact stresses through an appropriate geometry of the parts, and through the reduction of friction, while preventing adhesion. The lubricant is involved in this prevention process, mainly through the physical-chemical reactivity of its additives.

Generally sulfur, phosphorus, phosphorus-sulfur or borate anti-wear and extreme pressure additives are added in order to provide the transmission oils with properties that are protective against flaking. The other additives present in the lubricant can also have a positive or negative impact on the propagation of cracks within the parts and, therefore, on the flaking phenomenon.

In manual gearboxes, the presence of synchronizers induces additional stresses. In fact, these components include a cone and ring device between which the frictions have been specifically controlled: the friction must be sufficient to synchronize the gears, but the cone and the ring must be able to disengage, because otherwise the synchronizer lock.

In addition, if the friction level is not adapted to the geometry of the parts, wear occurs in the cone-ring assembly.

The friction level can be adjusted by adding friction modifiers to these gearbox oils.

Thus, in oils for manual gearboxes, anti-wear, extreme pressure additives and friction modifiers can coexist, all having an action on the surface of the parts and potentially having an effect on both the level of friction and the peeling phenomenon.

The formulation of oil for a manual gearbox having both high protection against flaking, preventing wear and blocking of synchronizers and allowing to easily change gears, is based on a specific selection and dosage of friction modifiers, extreme pressure additives and anti-wear.

It is known how to formulate lubricating compositions comprising organic molybdenum friction modifier compounds with organic phosphorus and / or organic sulfur and / or organic wear-resistant phosphorus-sulfur and extreme pressure compounds, in particular in order to improve anti-aging properties. wear of these oils.

US patent document US 6,806,241 discloses a lubricating composition comprising a molybdenum complex prepared by reacting 1 mole of a fat that can be a glyceride or a fatty acid, from 1 to 2.5 moles of diethanolamine, and a molybdenum source in an amount sufficient to obtain a complex containing from 0.1 to 12% by weight of molybdenum based on the weight of the complex, a thiadiazole compound and optionally a phosphorodithioate. No specific example is given of a composition comprising both molybdenum, in a mass content between 90 and 350 ppm, sulfur and phosphorus.

Patent application EP 0874040 discloses lubricants for internal combustion engines comprising a molybdenum complex prepared by reacting 1 mole of fat which can be a glyceride or a fatty acid, from 1 to 2.5 moles of diethanolamine, and a source of molybdenum in an amount sufficient to obtain a complex containing 0.1 to 12% by weight of molybdenum based on the weight of the complex, and an organic sulfur compound selected from thiadiazois dimercapts, bisditiocarbamates, dithiocarbamates, phosphorodithioates.

No indication is given on a specific combination of the molybdenum complex with one or more of the organic sulfur compounds mentioned, nor on the amount of Mo contained in the lubricating compositions. The examples indicate an amount of complex comprised between 0.5 and 1.5% by weight in the lubricant, which corresponds to a Mo content comprised between 5 and 1,800 ppm in the lubricant. Too strong or too low a Mo content is unsuitable for formulating a gearbox lubricant. In fact, the synchronization peeling and blocking problems can result from this. The same applies to the selection and dosage of sulfur and / or phosphorus-sulfur additives.

Patent application WO 2005035700 discloses lubricating compositions comprising an organic molybdenum compound selected from molybdenum dithiophosphates or dithiocarbamates and an anti-wear compound which may be a thiadiazole dimercapto. This application does not reveal the combination of a specific molybdenum content with the use of a thiazole as an anti-wear and extreme pressure agent.

The use of molybdenum in the form of dithiophosphates or dithiocarbamates is also capable of generating other problems of wear and / or blocking of the synchronizers, and possibly flaking.

However, prior art compositions based on molybdenum, sulfur and / or phosphorus refer to the field of antioxidants and anti-wear agents, mainly for formulating oils for internal combustion engines.

In particular, these prior art compositions do not have a specific dosage of the Mo element, and a sufficient presence of sulfur and phosphorus allowing them to have both the properties of protection against flaking, the wear of the synchronizers and avoiding the blocking of the synchronizers of a satisfactory manner. These compositions are therefore not adapted for the lubrication of motor vehicle gearboxes, in particular manual gearboxes.

Among the oils known for manual gearboxes, borate oils have an excellent compromise between the different properties listed above. These oils can be formulated without any sulfur, phosphorus or phosphorus-sulfur compounds, and until now no technology based on sulfur, phosphorus or phosphorus-sulfur additives has given the possibility of reaching the level of performance obtained with borates in relation to protection against the flaking and wear of the synchronizers.

In spite of its excellent extreme pressure performances and many advantages, the use of borates is, however, not desirable as there is a risk of contamination of the lubricant by water. In fact, inorganic borates being partially soluble in water, the amount of water present in the molecule can increase which has the effect of changing the structure of the borate. In the presence of a significant amount of water in the medium, the borate structure being modified in this way, can crystallize and form razor-like crystals with sizes greater than 100 nm. In this case, borates can block synchronization systems in gearboxes.

The use of borate oils, therefore, requires a particular design of the manual gearboxes with a waterproof system, which has complexity and a cost that would be desirably avoided.

Therefore, there is a need for car gearbox oils, in particular manual gearboxes, giving both protection against the peeling phenomenon in the gear teeth, allowing the wear of the synchronizers to be limited and preventing their blockage, allowing to change easily moving, and insensitive to water (they may not contain borates or even a reduced level of borates).

The object of the present invention are lubricating compositions, comprising an ester-amide molybdenum complex, combined with an extreme pressure additive containing sulfur and an extreme pressure additive containing phosphorus or phosphorus-sulfur and its use to lubricate gearboxes, in particular for automotive vehicles. A particularly relevant use is for manual gearboxes for motor vehicles.

BRIEF DESCRIPTION OF THE INVENTION

The object of the present invention is lubricating compositions comprising:

(a) An organic molybdenum compound, (b) One or more extreme pressure and anti-wear additives selected from tia (di) azois, (c) One or more extreme pressure additives and containing phosphorus and / or phosphorus anti-wear sulfur selected from phosphites, phosphates, phosphonates, thiophosphates or thiophosphites.

Said lubricant composition having a molybdenum mass content comprised between 90 and 350 ppm.

Preferably, the lubricating compositions according to the invention have a mass content of molybdenum comprised between 100 and 200 ppm, preferably between 140 and 180 ppm.

Preferably, the lubricating compositions according to the invention have a mass content of phosphorus comprised between 500 and 700 ppm, even more preferably between 520 and 650 ppm.

According to one embodiment, the lubricating compositions according to the invention comprise at least one thiophosphate, preferably at least one dithiophosphate, preferably at least one amino dithiophosphate, as a compound (c).

According to the preferred embodiment, the lubricating compositions according to the invention comprise at least one thiadiazole, preferably at least one thiadiazole dimercap as a compound (b).

The lubricating compositions according to the invention may comprise between 0.35% and 1% thiazole, preferably between 0.35 and 1% by weight of thiadiazole dimercapto.

According to a preferred embodiment, the lubricating compositions according to the invention comprise as a compound (a), at least one organic molybdenum complex, obtained by the reaction:

(i) a mono-, di, -, or triglyceride fat or type of fatty acid, (ii) an amine source of the formula (I) ^v x ² H _m (i) where X1 and X2 are both O or N, enem = 1 when X1 or

X2 is O, enem = 2 when X1 or X2 is N, (iii) a source of molybdenum selected from molybdenum trioxide or molybdates, preferably ammonium molybdate, in an amount sufficient to provide 0.1 to 20.0% molybdenum based on the weight of the complex.

Preferably, compound (ii) is diethanolamine or 2 (2aminoethyl) amino ethanol.

Preferably, fat (i) is a mono-, di- or triglyceride or fatty acids including from 4 to 28 carbon atoms, preferably from 8 to 18 10 carbon atoms, or a fatty acid including from 4 to 28 carbon atoms , preferably 8 to 18 carbon atoms.

According to a preferred embodiment, the molybdenum complex (a) consists of at least one of the following compounds, either alone or as a mixture:

where X1 and X2 are either O or N, and • n = 1 when X1 is oem = 1 when X2 is O, • n = 2 when X1 is N and = 2 when X2 is N, where R1 and R2 are fatty hydrocarbon chains comprising between 2 and 27 carbon atoms, preferably between 7 and 17 carbon atoms.

According to a preferred embodiment, the molybdenum complex (a) consists of at least one of the compounds corresponding to the following

formula: Z ° \ Z I laugh " ... κι Mo v \ /% \ / 0 ° (IV)

wherein R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms.

According to another preferred embodiment, the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula:

wherein R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms.

The present invention also relates to the use of the composition described above to lubricate gearboxes, in particular of motor vehicles.

According to a preferred embodiment, the present invention relates to the use of the composition described above to lubricate manual gearboxes, in particular manual gearboxes for motor vehicles.

DETAILED DESCRIPTION

Organic molybdenum compound: The lubricating compositions according to the invention can comprise any oil-soluble organic molybdenum compound, notably and not in a limiting way, molybdenum dithiophosphates and dithiocarbamates and various organic molybdenum complexes such as molybdenum carboxylates, esters , amides, which can be obtained by reacting molybdenum oxide or ammonium molybdates with fats, glycerides or fatty acids, or with fatty acid derivatives (esters, amines, amides ...).

Preferably, the lubricating compositions according to the invention comprise sulfur and phosphorus-free molybdenum complexes, with amide-type binders, mainly prepared by reacting a molybdenum source, which may, for example, be molybdenum trioxide, a amine and a fatty acid derivative, for example, comprising from 4 to 28 carbon atoms, preferably from 8 to 18 carbon atoms, such as, for example, fatty acids contained in vegetable or animal oils.

The synthesis of such compounds is, for example, described in US patents 4,889,647, EP0546357, US 5,412,130, EP1770153.

These organic molybdenum complexes can be obtained through the reaction:

(i) a mono, di, triglyceride or fatty acid type fat, (ii) an amine source of formula (I):

where X1 and X2 are either O or still N enem = 1 when X1 or X2 is O, enem = 2 when X1 or X2 is N, (iii) and from a molybdenum source selected from molybdenum trioxide or molybdates, preferably ammonia molybdate in an amount sufficient to provide 0.1 to 20.0% molybdenum based on the weight of the complex.

They generally comprise between 7 and 8.5% by weight of molybdenum based on the weight of the complex.

In particular, according to one embodiment, the organic molybdenum compound of the compositions according to the invention consists of at least one of the following compounds, alone or as a mixture:

(II)

where X1 and X2 are either O or N, and n = 1 when X1 is O in = 1 when X2 is O, n = 2 when X1 is N and = 2 when X2 is N, where R1 and R2 are chains of fatty hydrocarbons comprising between 3 and 27 carbon atoms, preferably between 7 and 17 carbon atoms.

According to one embodiment, the molybdenum complexes of the compositions according to the invention are prepared by the reaction:

(i) a mono-, di- or triglyceride acid or type of fatty acid, (ii) diethanolamine or 2- (2-aminoethyl) amino ethanol, (iii) and a molybdenum source selected from molybdenum trioxide or molybdates, preferably ammonia molybdate, in an amount sufficient to provide 0.1 to 20.0% molybdenum based on the weight of the complex.

In particular, according to one embodiment, the organic molybdenum compound of the compositions according to the invention consists of at least one of the following components (IV) or (V) alone or as a mixture.

H

(V) where R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms.

The content of the organic molybdenum compound in the compositions according to the invention is adjusted so that the content of the molybdenum mass of said compositions is comprised between 90 and 350 ppm, preferably between 100 and 200 ppm, even more preferably between 140 and 180 ppm .

A very low molybdenum content causes problems with synchronizer locking and potential wear of the synchronizer cone-ring assembly.

A very strong molybdenum content on the other hand has an unfavorable peeling effect.

Aunt (di) azois

Thia (di) azois are compounds that contain both a sulfur and a nitrogen atom in a five-atom ring. Benzothiazois are a particular type of thia (di) azois. This term of thia (di) azois includes, in addition to cyclic compounds containing one sulfur atom and one nitrogen atom per 5-atom ring, also thiadiazoles containing sulfur and two nitrogen atoms in such a ring.

These compounds can be unsubstituted or replaced by hydrocarbon compounds that increase their solubility in oil.

According to one embodiment, the thia (di) azois of the lubricating compositions according to the invention are unsubstituted thiadiazoles, thiazoles and benzothiazoles.

According to a preferred embodiment the thia (di) azois of the compositions according to the invention are dimercapto thiadiazoles, for example, 2,5dimercapto-1,3-4 thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 3,4dimercapto-1,2,4-thiadiazole, 4,5dimercapto1,2,3thiadiazole, 3methylmercapto-5mercapto-1,2,4-thiadiazole.

All of these components can be used alone or as a mixture.

Typically, thia (di) azois represent between 0.35 and 1% of the mass of the compositions according to the invention.

Preferably, the compositions according to the invention contain between 0.35 and 1% preferably between 0.34 and 0.45% by weight of thiadiazoles dimercapto.

Compounds containing phosphorus or phosphorus-sulfur:

The phosphorus-containing compounds of the lubricating compositions according to the present invention are extreme pressure and anti-wear additives such as phosphates, phosphites, or phosphonates. These terms both designate phosphoric acid, phosphorus, phosphines, their mono-, di- and tri-esters, for example, alkyl phosphates, alkyl phosphonates, alkyl phosphonates, and their salts, for example, amine salts.

The extreme pressure and anti-wear phosphorus-sulfur additives used in the present invention are (mono- or di) thiophosphates and thiophosphites, these terms including thiophosphoric and thiophosphoric acids, the esters of these acids, their salts, dithiophosphites or dithiophosphates.

According to a preferred embodiment, the extreme pressure and anti-wear phosphorus sulfur additives of the compositions according to the invention are thiophosphates, corresponding to formula (VI).

(VI) where X3 and X4 are independently of each other S or O, one of them at least being S, R3 and R4 are either hydrogen or alkyl groups having between 1 and 22 carbon atoms, M is a metal of groups IIA , III, VA, VIA, IB, VIB, VIII of the Periodic Table, n being the valence of said metal, or M is an ammonium formed from a primary, secondary or tertiary amine of the formula (R5) (R6) (R7) N, where R5, R6, R7 are either hydrogen or an alkyl group including from 1 to 18 carbon atoms and then n = 1.

More preferred compounds are dithiophosphates (X3 and X4 are sulfur), preferably zinc or an amine. Amine dithiophosphates are the most preferred compounds.

As phosphorus-sulfur examples of anti-wear and extreme pressure additives, mention may be made to monobutiltiofosfato, monooctiltiofosfato, monolauriltiofosfato, dibutiltiofosfato, dilauriltiofosfato, tributiltiofosfato, trioctiltiofosfato, trifeniltiofosfato, trilauriltiofosfato, monobutiltiofosfito, monoctiltiofosfito, monolauriltiofosfito, dibutiltiofosfito, dilauriltiofosfito, tributiltiofosfito, trioctyltophosphite, triphenylthiophosphite, trilaurylthiophosphite and salts thereof.

Examples of esters of triophosphoric acid and triophosphoric acid are those obtained by reaction with a nitrogen-containing compound such as ammonia or an amine, or zinc oxide or zinc chloride.

Preferably, the amount of these additives is adjusted so that the mass content of phosphorus in the oils according to the invention is comprised between 500 and 700 ppm, preferably between 520 and 650 ppm.

A very low content of extreme pressure and anti-wear element (sulfur and phosphorus) will cause scaling problems.

In addition, a very strong content of extreme pressure and anti-wear elements (as well as a friction modifier, including an organic molybdenum compound), will have an unfavorable effect on gear shifting: the friction coefficient of cone- ring will be very low, which prevents gear synchronization and therefore gear shifting.

In addition, it is desirable for environmental reasons to limit the sulfur and phosphorus content in lubricating compositions to what is necessary.

This, in combination with the molybdenum content of the lubricants according to the invention, gives the possibility to obtain both better anti-peeling, anti-wear properties of the synchronizer and avoid blocking of the synchronizer.

The most efficient agreement between these 3 properties therefore depends on a specific dosage of the friction modifier, anti-wear and extreme pressure compounds and therefore on the Mo, S, and P elements of these compounds.

Bases:

The compositions according to the invention can contain any type of animal or plant lubricant base, synthetic or natural, adapted for its use.

The base oil (s) used in the compositions according to the present invention may be oils of mineral or synthetic origin from groups I to V according to the classes defined in the API classification (or their equivalents according to ATIEL classification), as summarized below, alone or as a mixture.

Saturated product content Sulphur content viscosity index Group I Mineral oils <90% > 0.03% 80 <VI <120 Group II Hydrocracking oils > 90% <0.03% 80 <VI <120 Group III hydrocracking or hydro isomerized oils > 90% <0.03% > 120 Group IV Polyalphaolefins PAO Group V Esters and other bases not included in the bases of groups I to IV

The mineral-based oils according to the invention include all types of bases obtained through the vacuum and atmospheric distillation of crude oil, followed by refinement operations such as solvent extraction, de-asphalting, solvent dewaxing, hydro treatment, hydrocracking, hydro isomerization, hydro finishing.

The base oils of the compositions according to the present invention can also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins, the polyalphaolefins used as base oils, are, for example, obtained from monomers having 4 at 32 carbon atoms (eg octane, decene) and a viscosity of 100 ° C comprised between 1.5 and 15 cSt. Its average molecular weight is typically between 250 and 3,000. Mixtures of synthetic and mineral oils can also be used.

There is no limitation on the use of these and such a lubricant base to produce the compositions according to the invention, otherwise they must have properties, notably viscosity, viscosity index, sulfur content, resistance to oxidation adapted for use in a box gearbox, in particular, for motor vehicles, in particular a manual gearbox.

Preferably, the lubricating bases represent at least 50%, preferably at least 60%, or at least 70% by weight of the lubricating compositions according to the invention. Typically, they represent 75 and 90% by weight of the compositions according to the invention.

Preferably, the lubricating compositions according to the invention comprise Group I and / or III mineral bases, or Group IV synthetic bases according to the API classification.

Other additives:

The lubricating compositions according to the invention may also contain any type of additive adapted for their use, for example amine or phenol antioxidants such as diphenylamines, or phenols substituted in at least one of their ortho positions with alkyl groups, detergents, for example , sulfonates.

Agents to improve the viscosity index (augmentation agents VI) are preferably present in contents between 5 and 25% of the mass, in order to transmit viscosimetric properties adapted for use in a gearbox, in particular a gearbox of automobile, preferably a manual gearbox, such as, for example, polymethacrylates (PMA), polyisobutenes (PIB), or fatty acid esters.

Examples:

The mass compositions and performances with respect to synchronizer wear, synchronizer lock, flaking of the prepared lubricant compositions are shown in the present Table 1.

The peeling tests were performed under the following conditions:

Banco Sermes BCFP

Gearbox JR5-125 Renault, 1 pair of differentials 14x63, secondary axle 8200280045 and ring 8200280134, 3 pairs 28x37 of primary axles 8200107846 and intermediate pinions 3 ^o 7700114048

2.3 liters of oil, oil temperature 110 ° C

Input torque: 148 mN

Primary speed 3,000 rpm

Duration: 3 phases of 142 hours

Every 142 hours, the change of the primary axis, the intermediate pinion

3 ^o and the bearing supports.

Evaluation of the stripped surface:

Final score after 426 hours of the differential ring / pinion pair.

Score After 142 hours of 28x37 3 pairs primary axle / sprocket Intermediate 3

Depending on the score result of these parts, it is said to pass (satisfactory scores) or fail (very large skinned surface).

The tests to block the synchronizers were carried out in a cone-ring pair under the following conditions (procedure SINC-40):

54 mm filament metal ring, for example, ref 7700 708 152 or 7700 869 430

JXX intermediate pinion gearbox cone, rectified carbonitride steel coated in stone for example, ref 7700 867 612 or 7700 740 880

Oil: 250 ml of oil, oil level in the middle of the pinion and ring

SAE2 / A machine SAE / 2 synchronization adapter

I = 0.155 m ² / kg

N = 300 rpm

F = 60 daN

T = 6s (consecutive period between two consecutive braking operations) n = 10,125 shifting cycles (21 hours)

The synchronization lock test is approved if, during 10125 shifting cycles, the number of cycles in which the disengagement between the cone and the ring requires the application of a counter torque of more than 2 mN is a maximum of 100 cycles .

The synchronizer wear tests were performed on a cone-ring pair under the following conditions (procedure SINC-13, SAE 2-A)

54 mm filament metal ring, for example, ref 7700 708 152 or 7700 869 430

Cone of JXX gearbox of intermediate pinion, rectified carbonitride steel coated in stone for example, ref 7700 867 612 or 7700 740 880

Oil: 125 ml oil, oil level at the bottom of the ring

SAE2 machine / SAE2 synchronization adapter /

I = 0.155 m ² / kg

N = 600 rpm

F = 60 daN

T = 3.5s (consecutive period between two consecutive braking operations) n = 20,000 shifting cycles (20 hours)

At the end of these 20,000 cycles: the axial wear of the synchronizer / travel cone ring pair is measured in mm. It must be at most 0.30 mm in order to be acceptable (pass). A wear of less than 0.15 mm is an excellent performance. A wear of more than 1 mm is disqualifying (guard compensation).

Discussion:

Oils A and B are oils according to the invention: oils C and D are borate oils, sensitive to water.

A and B oils have a level of performance in terms of synchronizer wear, equivalent to that of borate oils, and pass the blocking and peeling tests in the same way.

Oil E contains the same anti-wear and extreme pressure additives as oil A, also with compounds containing phosphorus of the phosphite / phosphate type; this E oil does not contain any friction modifiers with molybdenum. Synchronizer wear is at an unacceptable level (0.84 mm).

The oils F, G, H have the same additives in the agents containing sulfur and phosphorus-sulfur anti-wear and extreme pressure as the oils according to the invention, but it contains several friction modifiers without molybdenum. The wear of the synchronizers is very significant with these oils.

Oils I and L have the same additives with respect to agents containing sulfur and sulfur-phosphorus anti-wear and extreme pressure as the oils according to the invention, and contain a friction modifier with molybdenum of the ester amide type.

The Mo ester content of the oil is 400 ppm, and this oil fails to scale.

The Mo mass content of oil L is 80 ppm, and this oil fails to block synchronization.

Oil J has the same additives as sulfur and phosphorus-sulfur-containing agents and extreme pressure as the oil according to the invention, but does not contain any molybdenum. A fatty acid monoester is present as a friction modifier. This oil fails in relation to the synchronizer block.

K oil has the same additives as sulfur and phosphorus-sulfur anti-wear agents and extreme pressure as the oils according to the invention, and does not contain any molybdenum. It does not contain any friction modifiers. This oil fails in relation to the synchronization block.

M and N oils do not contain any thiazole as a sulfur-containing compound. M oil is also free of molybdenum. These oils obtained a particularly catastrophic result in relation to flaking. It should be noted that these oils do not contain any thiadiazole dimercapto.

Table 1: composition and mass properties

O 1.00 0.40 06'0 0.90 21.00 4.80 71.00 O 610 Failed / 0.49 Approved 100.00 LL 1.00 0.40 0.90 0.90 21.00 4.80 71.00 O 610 Failed / 1.03 Approved 100.00 LLÍ 0.20 0.40 0.90 0.90 21.00 5.30 71.30 O 625 Failed / 0.84 Approved í 100.00 Q 8.70 19.50 71.80 Approved Approved / 0.14 Approved o o θ 'o O The b-_ 00 11.00 31.00 35.00 14.30 O Approved Approved / 0.08 Approved 100.00 m 0.20 0.35 0.85 0.80 9.00 61.50 I 20.00 7.30 160 535 Approved Approved Approved 100.00 < 0.20 O 0.90 0.90 21.00 4.80 71.80 160 610 Approved Approved / 0.12 Approved 100.00 Mo Complex Borate Additive Poly sulfide ester Fatty acid ester Fatty acid mono ester phosphates / phosphites thiadiazole dimercapto dithiophosphates antioxidant enhancer VI detergent Mineral Group I Mineral Group II i Synthetic Group IV Friction Modifiers Anti-wear and external pressure additives Others Bases ppm of Mo ppm of P I Flaking Wear / Value in mm Sync lock Total

Mo complex: a molybdenum complex with amide binders.

Continuation of Table 1: composition and mass properties

z: 0.20 1.90 1.20 11.00 The CM 76.50 00'8 ^! 160 Disapproved Approved Approved 100.00 1.90 1.20 11.00 1.20 76.70 8.00 Disapproved I Approved Approved 100.00 0.10 0.40 06'0 0.90 21.00 4.80 72.00 08 610 Approved / 0.22 Disapproved 100.00 0.40 0.90 0.90 21.00 4.80 72.00 O 610 Approved / 0.12 Disapproved o o o o "2 1.00 0.40 06'0 0.90 21.00 4.80 71.00 O 610.4 Approved / 0.20 Disapproved 100.00 0.50 0.40 0.90 06'0 21.00 4.80 72.00 400 610 Disapproved Approved / 0.13 ¹ Approved 100.00 1.00 0.40 0.90 0.90 21.00 4.80 71.00 O Failed / 0.75 Approved 100.00 | Mo Complex Borate Additive Poly sulfide ester Fatty acid ester Fatty acid mono ester phosphates / phosphites thiadiazole dimercapto dithiophosphates antioxidant augerVI detergent Mineral Group I Mineral Group II Synthetic Group IV Friction Modifiers Anti-wear and extreme pressure additives Others Bases ppm of Mo ppm of P Flaking Wear / I Value in mm ' Sync lock Total

Mo complex: a molybdenum complex with amide binders.

Claims (14)

1. Lubricating composition, comprising: (a) An organic molybdenum compound, (b) One or more extreme pressure and anti-wear additives selected from tia (di) azois, (c) one or more extreme pressure additives, containing phosphorus and / or phosphorus anti-wear sulfur selected from phosphites, phosphates, phosphonates, thiophosphates or thiophosphites; said lubricant composition having a mass content of molybdenum comprised between 90 and 180 ppm. The lubricating composition according to claim 1 having a mass content of molybdenum comprised between 100 and 200 ppm, preferably between 140 and 180 ppm. The lubricating composition according to one of claims 1 to 2, having a mass content of phosphorus comprised between 500 and 700 ppm, preferably between 520 and 650 ppm. The lubricating composition according to one of claims 1 to 3, comprising at least one thiophosphate, preferably at least one dithiophosphate, preferably at least one amine dithiophosphate, as compound (c). The lubricating composition according to one of claims 1 to 4 comprising at least one thiadiazole, preferably at least one thiadiazole dimercap as compound (b). The lubricating composition according to claims 1 to 5, comprising between 0.35% and 1% of thiazole, preferably between 0.35 and 1% of the mass of thiadiazole dimercapto. The lubricating composition according to one of claims 1 to 6, comprising, as a compound (a), at least one organic molybdenum complex, obtained by reaction: (i) from a mono-, di- or triglyceride fat or type of fatty acid, (ii) from an amine source of formula (I): where X1 and X2 are either O or N, and n and m = 1 when Χ1 or Χ2 is The enemy = 2 when X1 or X2 is N, (iii) and from a source of molybdenum selected from molybdenum trioxide or molybdates, preferably ammonium molybdate, in an amount sufficient to provide 0.1 to 20.0 % molybdenum based on the weight of the complex. The lubricating composition according to claim 7, wherein the compound (ii) is diethanolamine or 2- (2-aminoethyl) amino ethanol. 9. The lubricating composition according to one of the claims 7 to 8, in which fat (i) is a mono-, di- or triglyceride of fatty acids including from 4 to 28 carbon atoms, preferably from 8 to 18 carbon atoms, or a fatty acid including from 4 to 28 carbon atoms, preferably 8 to 18 carbon atoms. The lubricating composition according to one of claims 7 to 9, wherein the molybdenum complex (a) consists of at least one of the following compounds, either alone or as a mixture: H _n -1 (H) where X1 and X2 are either O or N, and n = 1 when X1 is O in = 1 when X2 is O, n = 2 when X1 is N and = 2 when X2 is N, in that R1 and R2 are fatty hydrocarbon chains comprising 5 between 3 and 27 carbon atoms, preferably between 7 and 17 carbon atoms. The lubricating composition according to one of the claims 7 to 9, where the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula: 10 where R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms. 12. The lubricating composition according to one of the claims 7 to 9, where the molybdenum complex (a) consists of at least one of the compounds corresponding to the following formula: (V) where R1 is a fatty hydrocarbon chain comprising between 3 and 27 carbon atoms, preferably between 7 and 27 carbon atoms. 13. Use of a composition according to one of the claims 5 1 to 12 for lubricating gearboxes, in particular for automotive vehicles. 14. Use according to claim 13, wherein the gearbox is a manual gearbox.