EP3622042A1

EP3622042A1 - Lubricant composition

Info

Publication number: EP3622042A1
Application number: EP18725407.3A
Authority: EP
Inventors: Stefan Seemeyer; Stefan Grundei; Carla KRUTZSCH; Philipp ALTMANN
Original assignee: Klueber Lubrication Muenchen SE and Co KG
Current assignee: Klueber Lubrication Muenchen GmbH and Co KG
Priority date: 2017-05-11
Filing date: 2018-04-19
Publication date: 2020-03-18
Anticipated expiration: 2038-04-19
Also published as: KR102270035B1; WO2018206252A1; CA3055493A1; EP3622042B1; US11427778B2; CA3055493C; JP7038794B2; US20210324287A1; JP6869372B2; CN110651028A; MX2019013354A; JP2020516748A; CN110651028B; KR20190114014A; US20200157454A1; DE102017004541A1; EP4219668A1; JP2021046563A; US11085004B2; BR112019019218A2

Abstract

The invention relates to a lubricant composition for application onto the surface of drive elements, the lubricant composition containing a base oil and a silasesquioxane. The composition is suitable for preventing, reducing or avoiding fatigue phenomena in the material of drive elements, such as gray staining, false brinelling and white etching cracks.

Description

Lubricant composition Description

The present invention relates to a lubricant composition for application to the surface of drive elements, such as rolling bearings, gears, plain bearings and chains. The composition is suitable for fatigue in the material of driving elements, such as

Preventing, lessening or preventing pitting, false brinelling and white etching cracks. Another object of the present invention is the use of the lubricant composition for

Treatment of surfaces of drive elements and the further use of such drive elements.

In the case of drive elements there are two types of damage in the case of excessive mechanical loads: 1) seizure and wear, in which the damage is caused by the

Surface of the contact surfaces emanates.

2) fatigue damage, which causes its output in the structure below the

contaminated areas and eventually lead to outbreaks such as gray pitting, false brinelling and white etching cracking. To reduce wear and tear there are a variety of

Additives and solid lubricants that are well known and widely used. To prevent fatigue damage very few effective measures are known. One measure is the increase of the lubricating film thickness.

Fatigue wear is caused by local overload of the material due to periodic compressive stress. The fatigue of the material becomes visible through gray staining, surface fatigue, micro-pitting or pits on the surface of the material. As a rule, initially 20 to 40 μm below the surface, there are fine cracks in the metal mesh, which lead to material eruptions. The small microscopically visible eruptions on the tooth flank, referred to as micro-pittings or pitting, can be recognized macroscopically as dull gray areas. In the case of gears, gray spots on tooth flanks can generally be observed in virtually all speed ranges. Even in rolling bearings very shallow eruptions occur in the area of the sliding contact as gray patches on the track. These relationships are described in detail in DE 10 2007 036 856 A1 and the literature cited therein.

White etching cracks (WEG) can cause fatigue damage that occurs much sooner than with a drive element

Loading parameters is expected. Metailographically, white cracks in the depth of the microstructure can be detected. The white discoloration is based on the fact that the appearing as white cracks are not subject to the etching required in the sample preparation. These cracks can lead to outbreaks in the material and failure of the component with further tribological stress. As a cause, several factors such as slippage, harmful currents and diffused hydrogen are discussed. As is known, such damage occurs in particular in warehouses of

Electric motors or generators of wind turbines and in the

Automotive sector (see also dissertation H. Surborg, 2014, Otto von Guericke University Magdeburg, Shaker Verlag Aachen 2014).

False brinelling is a form of damage that occurs in seemingly stationary bearings. Vibrations (for example in machines but also during transport by motor vehicles, rail vehicles or ships) or elastic deformations micro-movements are introduced into the contact surfaces, which can lead to damage after a few load changes. This can lead to restless running behavior and to immediate or early component failure.

In principle, the damage mechanism described above is one of the most serious due to the resulting cracks

Material impairments.

To avoid these fatigue damage, the following measures are usually taken in practice:

- reduction of contact forces,

- suitable choice of lubricant,

- sufficient lubricant supply,

- favorable positioning and design of the lubrication points,

- Avoiding conditions without lubrication.

Furthermore, to improve the viscosity properties in

Lubricants used different additives to avoid or at least minimize the above-mentioned damage in rolling bearings, gears, gears and the like. In addition, various studies have been made to avoid fatigue, including an attempt to improve the lubricity of lubricants by adding various additives. In particular, additives have been investigated which can reduce the friction between the components or which have an improved viscosity.

Thus, DE-OS 1 644 934 describes organophosphates as additives in

Lubricants added as anti-fatigue additives.

The above-mentioned DE 10 2007 036 856 A1 discloses the addition of polymers with ester groups which are used as antifatigue additives in lubricants. US 2003/0092585 A1 discloses thiazoles as additives which

Can prevent damage to surfaces.

EP 1 642 957 A1 relates to the use of MoS2 and

Molybdenum dithiocarbamate, which are used as additives in urea fats for cardan shafts.

The additives known from the prior art described above, such as organophosphates and thiazoles, are not thermally stable as organic substances. In addition, they can evaporate under the operating conditions or can be used as classic anti-wear additives especially with the

Metal surfaces react, d. H. They react predominantly on the touching roughness peaks, since there by the occurring

Flash temperatures sufficient energy for a chemical reaction with the metallic friction layer is present. Therefore, you can at least counteract fatigue damage in a subordinate manner. Solid lubricants, such as Molybdenum disulphide, on the other hand, tends to settle out of oil formulations due to their density and can also be corrosive. Since the solid particles are used with particle sizes in the micrometer range, there is a strong influence on the flow behavior and an increase in viscosity and a deviation from the Newtonian

Flow behavior. This behavior degrades the availability of the additive in the lubrication gap. SEM investigations on the surfaces of the metallic friction partners show that these structures have depressions with dimensions well below 1 μm. These depressions are the

Solid lubricant particles with sizes in the micrometer range not accessible.

DE 10201 1 103215 A1 describes the use of a composition comprising surface-modified nanoparticles and a carrier material which is applied to the surfaces of drive elements for the purpose of preventing or preventing the onset of wear

Reduction of fatigue damage is applied. It is believed that the mechanism of action of the nanoparticles is based on their ability to attach to and smooth the surface of the drive elements. The smoothing increases the contact surfaces and reduces the surface pressure.

JP 2006144827 A mentions compositions with silica nanoparticles for the suppression of WEC damage.

A disadvantage of the in DE 10201 103215 A1 and JP 2006144827 A

that it is above the available

Techniques often difficult to effect sufficient occupancy of the OH groups on the surface of the nanoparticles. This can lead to stability problems during storage. In addition, the entry of air can lead to foaming. Finally, filtering the lubricant may cause filtration problems. Starting from the state of the art, it is the object of the present invention to provide a lubricant composition which can be applied to the surfaces of drive elements so as to prevent, reduce or increase fatigue phenomena such as pitting, false brinelling and white etching cracks avoid, and at least partially eliminates the aforementioned disadvantages occurring in the prior art.

The subject of the present invention is a

Lubricant composition for application to the surface of

Driving elements, wherein the lubricant composition contains a base oil and a silsesquioxane. The composition is suitable for

Fatigue phenomena in the material of drive elements, such as

Preventing, lessening or preventing pitting, false brinelling and white etching cracks. The positive influence of

Lubricant composition is surprising, since silsesquioxanes significantly smaller than those in the publications DE 10201 1 103215 A1 and

JP2006144827A described nanoparticles are and therefore could not be assumed that they can cause a reduction in the fatigue phenomena analogous to these particles via a surface smoothing.

In practical experiments it was found that the inventive

Composition can be homogeneously mixed with base oils of different polarities, since, for example, the choice of the substituents of Siiasesquioxans the polarity of the composition can be easily adjusted. In addition, due to its manufacturing process, sufficient saturation of the OH groups of the Siiasesquioxans can be ensured. Furthermore, it was found that the use of

Siiasesquioxan allows a high storage stability, as well as that it does not contribute to any Impairment of the foam behavior or the filterability comes. In practical experiments it has also been found that silsesquioxanes which are liquid at room temperature (20 ° C) and / or low melting points

(preferably below 100 ° C, DIN EN ISO 1 1357-2 (Issue: 2014-07)), can be used favorably.

Silasesquioxanes (also called silasesquisiloxanes, sesquisiloxanes or silesquioxanes) are organosilicon compounds and form cage-like structures with Si-O-Si bonds and tetrahedral Si corners. The silsesquioxane may have in molecular form 6 to 12 Si corners and / or be present as oligomer and / or polymer. Preferred according to the invention are molecular ones

Silsesquioxanes, more preferably molecular silsesquioxanes of 6 to 12, more preferably 7 to 10, especially 7 or 8 Si corners. In this case, in a preferred embodiment, each Si center is bonded to three oxo groups, which in turn connect to other Si centers.

In another preferred embodiment, the Si centers are only partially attached to three oxo groups attached to other Si centers, and preferably three, Si centers are attached to only two oxo groups attached to other Si centers. The third group is here preferably a substituent, more preferably a hydroxy substituent.

The fourth group on Si is also preferably a substituent, whereby a surface-modified silsesquioxane can be obtained, which is preferred according to the invention. Suitable substituents are, for example, alkyl (C1-C20), cycloalkyl (C3-C20), alkenyl (C2-C20), cycloalkenyl (C5-C20), alkynyl (C2-C20), cycloalkynyl (C5-C20) -, aryl (C6-C18) - or

Heteroaryl group, oxy, hydroxy, alkoxy (C4-C10), oxirane polymer

(Degree of polymerization with 4 to 20 repeating units), carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, Alkoxysilylalkyl, alkylsilySaSkyl, halogen, epoxy (C2-C20), ester, aryl ether, fluoroalkyl, blocked isocyanate, acrylate, methacrylate, mercapto, nitrile, amine, and / or phosphine group, each substituted or unsubstituted. The silsesquioxane may have the same substituents or mixtures of different substituents.

Preferred substituents are hydroxy, alkyl (C4-C10), aryl (C6-C12), in particular phenyl and tolyl, alkoxyl (C4-C10), alkenyl (C2-C10), oxirane polymer, in particular polyethylene glycol, polypropylene glycol, polybutylene glycol and / or their copolymers (degree of polymerization 4 to 20, in particular 10 to 15 repeating units), epoxy (C 2 -C 10), and / or cycloalkyl (C 5 -C 10), in each case substituted or unsubstituted.

Particularly preferred substituents are hydroxy, alkyl (C4-C10), phenyl, tolyl, alkoxyl (C4-C10), alkenyl (C2-C10) and / or oxirane polymer,

in particular polyethylene glycol, polypropylene glycol and / or their

Copolymers (degree of polymerization 4 to 20, especially 10 to 15

Repeating units), each substituted or unsubstituted. In a further embodiment of the invention, R can additionally contain functional groups, in particular thio groups, phosphate groups individually or in groups

Combination have. The optional existing thio or

Phosphate groups can additionally undergo a reaction with the metal surface to be protected.

According to the invention, the silsesquioxane can also be mixtures of structurally different silsesquioxanes.

Silasesquioxanes, for example, by hydrolysis of

Organotrichlorosilanes are synthesized (idealized: 8 RSiCl ₃ ; + 12 H ₂ 0 [RSi0 _{_3/2]} 8 + 24 HCl). Depending on the substituent (R), the exterior of the cage can be further modified. When R = H, the Si-H group may be one

Hydrosilylation or oxidation to SiSanol be subjected. Bridged poly-silsesquioxanes are most easily prepared from clusters containing two or more trifunctional silyl groups attached to non-hydrolyzable silicon-carbon bonds. Vinyl-substituted

Silasesquioxanes can be linked by alkene metathesis.

In a preferred embodiment, the silsesquioxane the chemical formula [RSi0 _3/2] _n in where: n = 6, 8, 10, 12; preferably n = 8, 10, 12 and especially 8, where R independently of one another = alkyl (C 1 -C 20) -, cycloalkyl (C 3 -C 20) -, alkenyl (C 2 -C 20) -, cycloalkenyl (C 5 -C 20) -, alkynyl (C2-C20), cycloalkynyl (C5-C20), aryl (C6-C18) or heteroaryl group, oxy, hydroxy, alkoxy (C4-C10), oxirane polymer (degree of polymerization having 4 to 20

Repeat units), carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy (C2-C20), ester, aryl ether, , Fluoroalkyl, blocked isocyanate, acrylate, methacrylate, ercapto, nitrile, amine, and / or phosphine group, each being substituted or unsubstituted.

The radicals R may be the same or different.

R is independently of one another = hydroxyl, alkyl (C 4 -C 10), aryl (C 6 -C 12), in particular phenyl and tolyl, alkoxyl (C 4 -C 10), alkenyl (C 2 -C 10), oxirane polymer, in particular polyethylene glycol, polypropylene glycol,

Polybutylene glycol and / or copolymers thereof (degree of polymerization 4 to 20, in particular 10 to 15 repeat units), epoxy (C2-C10), and / or Cylcoalkyl (C5-C10), in each case substituted or unsubstituted. R is particularly preferably independently of one another = hydroxyl, alkyl (C4-C10), phenyl, toyl, alkoxyl (C4-C10), alkenyl (C2-C0) and / or oxirane polymer, in particular polyethylene glycol, polypropylene glycol and / or their

Copolymers (degree of polymerization 4 to 20, especially 10 to 15

Repeating units), each substituted or unsubstituted.

In a further embodiment of the invention, R can additionally contain functional groups, in particular thio groups, phosphate groups individually or in groups

Combination have. The optional existing thio or

In a further preferred embodiment, the silsesquioxane has a structure which is derived from the chemical formula [RSiO _{_3/2]} n in which one or more, preferably one unit RSi silicon is replaced by other units. This silsesquioxane preferably has the formula

[RSiO _3/2] _n (R ₂ SiO) 3, where the radicals R may independently be selected from those described above and n = 2, 4, 6, 8, preferably n = 2, 4, 6 and especially 4 is.

Also conceivable is the use of bridged molecular

Silasequioxanes.

In a particularly preferred embodiment, the silsesquioxane is a silasesquioxane according to the formula (I):

where: R independently of one another = oxirane polymer, preferably

Polyethylene glycol, polypropylene glycol, polybutylene glycol and / or copolymers thereof (degree of polymerization with 4 to 20, preferably 10 to 15

Repeating units) and in particular -CH ₂ CH ₂ (OCH ₂ CH ₂ ) mOCH 3 and m = 10 to 15, in particular 13.3, wherein the silsesquioxane is optionally in the form of a mixture with other silsesquioxanes. Such silasesquioxane is in the form of a mixture with other silsesquioxanes, for example, available under the trade name: PEG POSS ^® from Hybrid Plastics Gage Mixture. In a further particularly preferred embodiment that is

Silsesquioxane a silasesquioxane according to the above formula (I), wherein: R independently of one another = alkyl (C 4 -C 10), aryl (C 6 -C 12), preferably isooctyl, isobutyl and / or phenyl, in particular iso-octyl, the

Silasesquioxane optionally in the form of a mixture with others

Silasesquioxanes present. Such silasesquioxane is in the form of a mixture with other silsesquioxanes, for example, available under the trade names: isooctyl POSS ^® Gage Mixture and Octalsobutyl POSS ^® from Hybrid Plastics. In a further particularly preferred embodiment, the silsesquioxane is a silsesquioxane according to the formula (II):

d l)

where R independently of one another = alkyl (C4-C10), preferably iso-octyl. Such a silsesquioxane is available, for example, from

Trade names: TriSilanollsobutyl POSS ^® from Hybrid Plastics.

It has been found that the lubricant composition can also contain mixtures of structurally different silsesquioxanes.

In a further preferred embodiment, the silsesquioxane is present on nanoparticulate carrier materials, preferably on oxidic nanoparticles, in particular on amorphous silicon dioxide nanoparticles. such

Silasesquioxanes are available, for example, under the trade name

POSS ^® Nanosilica Dispersion from Hybrid Plastics. An advantage of this is the very good stabilization of the nanoparticles in various media and the

Combination of the two different particle sizes. The silsesquioxane can be mixed directly with the base oil of the lubricant or in the form of a premix. In the case of incorporation in the form of a premix, this advantageously contains a support material, preferably selected from the group consisting of mineral oils, synthetic hydrocarbons, including particularly preferred

Polyalphaolefins (PAO) and metallocene-catalyzed PAO (m-PAO), Polyglycols, esters, perfluoropolyethers (PFPE), silicone oils, native oils and

Derivatives of native oils, aromatics-containing oils such as phenyl ethers, alkylated naphthalenes and the mixtures of the abovementioned support materials. Particular preference as a support material PoSygkykole, esters and synthetic hydrocarbons are used.

The base oil of the lubricant composition is preferably selected from the group consisting of polyglycols, silicone oils, PFPE, mineral oils, esters, synthetic hydrocarbons, most preferably including PAO, m-PAO, aromatic containing oils such as phenyl ethers

Diphenyl ethers, alkylated naphthalenes, phenyl ethers, native oils and

Derivatives of native oils, and the mixtures of the above-mentioned base oils. Especially preferred as base oil are polyglycols, esters and / or synthetic hydrocarbons, among which particularly preferred

Poiyaiphaolefine (PAO) and metallocene catalyzed PAO (m-PAO) used. Particularly preferred esters are selected from an ester of a

aliphatic or aromatic di-, tri- or tetracarboxylic acid (preferably C ₆ - to C ₆ cr) with one or in mixture C ₇ - to C ₂ 2 alcohols, from an ester of trimethylolpropane, pentaerythritol or dipentaerythritol with aliphatic C ₇ - to C22 carboxylic acids, from cis-dimer acid esters with C ₇ - to C 22 alcohols, complex esters, as individual components or in any mixture.

The lubricant composition may also contain other conventional additives, e.g. Thickeners (metal soaps, metal complex soaps, bentonites,

Ureas, silicates, sulfonates, polyimides, etc.), solid lubricants (PTFE, metal oxides, graphite, boron nitride, molybdenum disulfide, etc.) and additives (phosphates, thiophosphates, aromatic amines, phenols, sulfates, etc.).

Preferred thickeners are lithium soaps, lithium complex soaps, ureas, calcium complex soaps, calcium sulfonate thickeners, bentonites, AluminiumkompSexseifen. Particularly preferred thickeners are lithium soaps, lithium complex soaps, aluminum complex soaps, bentonites and ureas.

The additives mentioned may be soluble additives, in particular as

Corrosion inhibitor, as a friction reducing agent, as a means of protection against metal influences and as UV stabilizers.

For gear applications, it has proven to be particularly advantageous if the lubricant composition has a viscosity of ISO VG 68-680, particularly preferably ISO VG 220-460. In this case, the base oils used are preferably polyglycols on the one hand and on the other hand mixtures of synthetic hydrocarbons, including more preferably mixtures of PAO with m-PAO, mixtures of esters or compositions containing mixtures of synthetic hydrocarbons and esters as base oils. Also suitable are medicinal white oils.

For grease-lubricated applications in wind turbines, it has proven to be particularly advantageous if the lubricant composition has a NLGI class according to DIN 51818 of 0 to 3, preferably 1 or 2. In this case, the base oil preferably has a viscosity in the range 50 to 460 mm ² / sec. Preferably used base oils are PAO, m-PAO, esters and mixtures thereof. Preferred thickeners are lithium soaps, lithium complex soaps and ureas. For applications in the automotive sector, it has proved to be particularly favorable if the lubricant composition has a NLGI grade according to DIN 51818 of 1 to 3. Preferably used base oils are mineral oils, PAO, m-PAO, esters and mixtures thereof. Preferred thickeners are

Lithium soaps, lithium complex soaps, calcium complex soaps and ureas. In this case, the base oil preferably has a viscosity in the range 30-300 mm ² / sec, preferably in the range 50-200 mm ² / sec.

The lubricant composition preferably contains the silsesquioxane in an amount of from 0.01 to 40% by weight, more preferably from 0.05 to 20% by weight, still more preferably in an amount of from 0.07 to 15% by weight, and especially from 0, 1 to 10 wt.%, Based on the total weight of

Lubricant composition. In a further preferred

Embodiment, the lubricant composition contains the

Silasesquioxane in an amount of 0.05 to 5 wt.%.

The lubricant composition preferably contains the base oil in an amount of 99.99 to 50% by weight, more preferably 99 to 60% by weight, and more preferably in an amount of 98 to 65% by weight, based on

Total weight of the lubricant composition.

In a particularly preferred embodiment of the invention, the lubricant composition contains polyglycol as a base oil in combination with a silsesquioxane of the formula with: n = 6, 8, 10, 12, preferably n = 8, 10, 12 and in particular 8, where R independently of one another = oxirane

Polymer, in particular polyethylene glycol, polypropylene glycol and / or copolymers thereof (degree of polymerization 4 to 20, in particular 10 to 15

Repeating units). Also conceivable combination of polyglycol is as Basisöi with a silsesquioxane of the formula [RSi0 _3/2] n (R ₂ SiO) 3, with n = 2, 4, 6, 8, preferably n = 2, 4, 6 and especially 4 where R independently of one another = alkyl (C4-C10), preferably iso-octyl. Particularly preferred is the combination of polyglycol as a base oil with PEGPOSS ^® Cage Mixture.

In a further particularly preferred embodiment of the invention, the lubricant composition esters, hydrocarbons, alkylated diphenyl ethers containing as the base oil in combination with a silsesquioxane according to the formula [RSi0 _{_3/2]} _n with n = 6, 8, 10, 12, preferably n = 8, 10, 12 and in particular 8, wherein: R = alkyl (C1-C20) -, or aryl (C6-C18) -, more preferably iso-octyl, iso-butyl and / or phenyl.

In a further particularly preferred embodiment of the invention, the lubricant composition contains esters, hydrocarbons, alkylated diphenyl ethers as base oil in combination with a silsesquioxane according to the above formula (I), wherein: R = iso-octyl or iso-butyl and / or phenyl.

Particularly preferred is the combination of esters, hydrocarbons, alkylated diphenyl ethers as the base oil with IsooctylPOSS ^® Cage Mixture, PhenylPOSS ^®, ^® is OctalsobutylPoss.

The composition of the invention generally contains

Silasesquioxane in an amount of 0.01 to 40% by weight, more preferably from 0.05 to 20% by weight, still more preferably in an amount of 0.07 to 15% by weight, and especially from 0.1 to 10% by weight. %; Base oil in an amount of 99.99 to 50% by weight, more preferably in an amount of 99 to 50% by weight, still more preferably in an amount of 99 to 60% by weight, especially in an amount of 98 to 65% by weight. %; Thickener in an amount of 3 to 40 wt.%, More preferably in an amount of 5 to 40 wt.% And in particular in an amount of 7 to 25 wt.% And solid lubricants in an amount of 0 wt.% To 30 wt. %, more preferably in an amount of 0 to 20% by weight, and additives in an amount of 0% to 15% by weight, more preferably in an amount of 0 to 10% by weight, and more preferably in an amount of 2 to 10 wt.%, In each case based on the total weight of

Lubricant composition.

In a preferred embodiment of the invention, the

Lubricant composition:

From 5 to 80% by weight, preferably from 10 to 80% by weight, more preferably from 20 to 70% by weight and in particular from 25 to 60% by weight

Polyalkylene glycol, preferably selected from the group consisting of randomly distributed polyoxyethylene and / or

Polyoxypropylene units and / or other polyoxyalkylene, a block polymer of polyoxyethylene and / or

Polyoxypropylene units and / or other polyoxyalkylene, as a base oil and / or

Carboxylic acid ester as a base oil and / or

From 2 to 80% by weight, preferably from 10 to 80% by weight, more preferably from 20 to 70% by weight and in particular from 25 to 60% by weight

Fatty alcohol ethoxylates as base oil,

more than 10% by weight, preferably from 15 to 85% by weight, more preferably from 20 to 60% by weight and in particular from 25 to 50% by weight of water,

From 0.01 to 40% by weight, more preferably from 0.05 to 20% by weight, even more preferably from 0.07 to 15% by weight and / or from 0.05 to 5% by weight and / or from 0, 1 to 10 wt.% Silasesquioxane, wherein the amounts given in each case on the total weight of

Lubricant composition are related. Because of its water content, this lubricant composition can be considered as a water-based lubricant composition.

In a preferred embodiment of the invention is the

Lubricant composition as a water-based gear oil formulation, with which when performing a FZG test according to DIN ISO 14635-3 the

Power level 12 with total wear on the wheel and pinion of <150 mg is passed and preferably no significant additional wear is generated at subsequent extended test of 50 hours at power level 10.

Preferred base oils for the water-based lubricant composition are water-soluble polyalkylene glycols, water-soluble carboxylic acid esters and / or water-soluble fatty alcohol ethoxylates. Here, by "water-soluble" according to the invention to understand that after mixing the base oils with water (stirring for 1 hour) in a concentration ratio of at least 5 wt.% Base oil in water at room temperature (25 ° C) is a transparent liquid.

Particularly preferred carboxylic ester base oils for the water-based lubricant composition are selected from the group consisting of ethoxylated mono- or dicarboxylic acids having a chain length of C ₄ to C 40 and degrees of ethoxylation of 2-15.

Preferred fatty alcohol ethoxylates consist of fatty alcohols with chain lengths of C ₆ to C 22 and a degree of ethoxylation of greater than 3.

Preferred additives for the water-based lubricant composition are selected from the group consisting of: 0.5 to 20 wt.%, Preferably from 0.5 to 10 wt.%, Foaming or non-foaming emulsifiers from the class of anionic, nonionic or cationic surfactants, preferably selected from the group consisting of aliphatic or aromatic ethoxylates, carboxylates, sulfonates , Sulphates or ammonium salts,

From 0.5 to 50% by weight, preferably from 1 to 10% by weight, of antifreeze selected from the group consisting of alkylene glycol, glycerol or ionic liquids,

From 0.5 to 20% by weight, preferably from 5 to 20% by weight,

Corrosion additives selected from the group consisting of

Alkanolamines, phosphoric acid and carboxylic acid derivatives,

From 0.001 to 2% by weight, preferably from 0.01 to 1% by weight, of anti-foaming additives selected from the group

consisting of polydimethylsiloxane and acrylate polymers,

From 0.05 to 10% by weight, preferably from 1 to 5% by weight, of water-soluble scavenging and wear protection agent selected from the group

consisting of sulfur or phosphorus-containing compounds,

From 0.001 to 0.5% by weight, preferably from 0.05 to 0.4% by weight, of biocides selected from the group consisting of substituted

Isothiazolinones and Bronopol, and mixtures thereof.

In a further preferred embodiment of the invention, the water-based lubricant composition contains 0.5 to 40% by weight.

Lubricant thickener selected from the group consisting of metal soaps from mono- and / or dicarboxylic acids, ureas, phyllosilicates,

Solid lubricants and Aerosil.

In a preferred embodiment of the invention is the

Lubricant composition as gear oil formulation with which, when performing a FZG Graufleckentests C / 8.3 / 60 according to FVA information sheet 54/7 with injection lubrication the profile deviation in the step run 7.5 pm and / or in the endurance 20 pm does not exceed. In a preferred embodiment of the invention, the

Lubricant composition characterized in that when performing a false brinell test using SNR FEB 2 tester at room temperature, 8000 N load, swivel angle 3 ° and 24 Hz oscillation frequency has a running time of at least 50 h, and the wear of the drive element is preferably below 100 mg, especially below 20 mg.

In a further preferred embodiment of the invention, the lubricant composition is characterized in that a mass loss of the drive element due to vibrations by at least 50%,

preferably reduced by at least 90% and / or the time to failure is at least doubled.

Another object of the present invention is the use of the lubricant composition according to the invention for the treatment of surfaces of drive elements, preferably of rolling bearings, gearboxes, plain bearings and / or chains, in particular rolling bearings and gearboxes.

Also suitable is the lubricant composition according to the invention for lubricating seals on rotating shafts. Particularly advantageous is the use in rolling bearings, which are used as wheel bearings and / or gears that are exposed to vibration. Also particularly advantageous is the use in main bearings, blade bearings, pitch bearings, generator bearings of wind turbines. Particularly advantageous is the application in rolling bearings, which are used in electric motors of electrically powered vehicles. Particularly advantageous is the use in rolling bearings in clutches, especially at

Hybrid vehicles. Also particularly advantageous is the use in bearings in ancillary equipment both in industrial plants and in automobiles. Bearings in ancillary units are characterized by the fact that the ancillaries are generally not operated continuously but only temporarily switched on and thus act vibrations on the stationary bearings. Auxiliary units in automobiles are also frequently driven by Pulley. Also particularly advantageous is the use in joints in automotive applications such as constant velocity joints, Azipod

Joints, tripod joints, suspension joints and / or ball joints where material fatigue / breakouts are also known as damage.

The abovementioned drive elements are particularly susceptible to the damage mechanisms described above, so that the use of silsesquioxanes with their advantageous influence on them is particularly efficient.

Also particularly preferred is the treatment of surfaces of

Drive elements in machines and conveyor systems used for the production of

Be used in foods where direct contact of the

Lubricant composition with the food possible and an appropriate food approval of the

Lubricant composition is required (USDA or NSF, Kosher, Halal). Another object of the present invention is the use of drive elements, preferably rolling bearings, gears, plain bearings and / or chains whose surfaces with the inventive

In plant and machinery for the production and promotion of food, in wind turbines, in automobiles, in Pulleylagern, in rail vehicles, in ships, in

Electric motors, generators, ancillaries, joints.

Test methods used: The SNR-FEB 2 (False-Brinelling test rig of the rolling bearing company SNR) determines the wear behavior of lubricant compositions in rolling bearings with small oscillating rolling and sliding movements with a constant load. The Abschaitkriterium the SNR is the wear path. If the value exceeds 30 mm for a bearing, the run is automatically ended or the specified runtime is reached. The bearing type FAG 51206 is used as a test bearing. The resulting wear is not determined by the wear path but by weighing the cleaned bearing rings before and after the test. The grooves of the bearing rings are filled completely with the lubricant composition to be tested, excess grease is scraped off. This results in an amount of lubricant composition of about 1 g per bearing ring depending on the density.

Flender foam test GG-V 425 Rev.

The test device consists of a closed gear housing with lens. There are two equal gears (outer diameter 54 mm) mounted centrally above vertical shafts that dip into the test oil so that part of the gears are not covered by oil. At a speed of 1450 rpm, the gear pair is driven for 5 min. As it were air is mixed into the oil. The change / increase in volume can be documented via a scale placed in the viewing window. Limits of the standard are: after 1 min style after the operation of the gear pair <15% and after 5 min style <10% total. Foam volumes must not be exceeded. viscosity

Viscosity measurement (DIN 51562) using a Stabinger viscometer SVM 3000 (Anton Paar).

Foam test ASTM D 892

In the method, air is foamed at room temperature, then at 94 ° C and then again at room temperature for 1 min at a constant volume flow through a submerged sintered ball. It is measured a) how much foam in ml is formed and b) how long it takes until the foam has degraded again after the completion of the introduction of air. Indication is (a, b). Limit value: (maximum 75 ml / 10 min) for all 3 temperature sequences must not

are exceeded, b is given in the form x: y min. This means the foam has dissolved after x minutes and y seconds.

Pitting test

C / 8.3 / 60 according to FVA information sheet 54/7 with injection lubrication. The

Limit values of the standard are: The profile deviation may not exceed 7.5 μηι during the step run and 20 μιη during the endurance run. In some cases the test was carried out differently at 90 ° C and splash lubrication. FZG test method A / 2,8 / 50 for the determination of relative creep resistance and wear behavior of gear fluid greases

Performance according to DIN ISO 14635-3 standard with splash lubrication. Limits of the standard are:

Achieved power level = sum of the damage (width of all grooves and eaters) on the active tooth flanks of the 16 pinion teeth is more than one tooth width or 20 mm. Additionally evaluation of wear on wheel and pinion.

In addition, here after the end of the test, a prolonged test was carried out over a period of 50 h at force level 10 with determination of the wear on the wheel and pinion.

Filtration test:

A heatable oil reservoir (60 ° C) is filled with approx. 10L of oil, controlled by a controllable pump (Vogel Fluidtec GmbH / Flow Sensor), the oil in a circle (6L / min) through a filter with a well-defined pore size (Mahle PI 2105 PS 3μηι / Mahle PI 3105 PS 10μηι) pumped. Before and after the filter, the pressure is measured by sensors. The system switches off when the pressure difference exceeds 2.2 bar. The test duration is up to 840 h. Example 1: Testing to improve false brinell protection

A lithium soap grease of NLGI grade 2 with polyglycol base oil with about 46 mm ² / sec viscosity at 40 ° C and additive package (corrosion, oxidation stability, load carrying capacity, wear) was mixed with 5.85% PEGPOSS ^® Cage Mixture and mixed with a Speedmixer (Fa House shield, type DAC 700.1 FVZ) homogenized (example fat 1). PEGPOSS ^® Cage Mixture has a viscosity of approx. 80 mmVsec at 40 ° C. To compensate for the dilution effect, a comparison fat 1 was prepared in which the fat 5.85% of a polyglycol based on EO: PO about 1: 1 with comparable viscosity was diluted and homogenized in the same way. Both greases were exposed to the SNR FEB 2 test rig at 8000 N load, a swivel angle of 3 °, a vibration frequency of 24 Herz at 20 ° C. The example fat 1 reaches the intended

Test duration of 50 h with low mass loss of the bearings. Comparative grease 1, on the other hand, reaches the maximum permissible wear after approx. 19 h, the run must be stopped.

Example Grease 1, PG Grease, Comparison Grease 1, PG Grease, Lithium Soap, PG Base Oil + Lithium Soap, PG Base Oil + Diluted at 5.85% Diluted with 5.85% PG PEGPOSS ^® Cage Mixture Base Oil

Wear bearing 1 (mg) 21 95

Wear bearing 2 (mg) 0 216

Test duration 50 h 19 h, 28 min (demolition)

Example 2: Effect of silsesquioxane to suppress the formation of pitting in an ester oil for transmissions

The results show that arise in the gear oil Esterbasis upon addition of IsooctylPOSS ^® no changes in the kinematic viscosity and foaming behavior. The training of the gray patches On the other hand, the addition of IsooctylPOSS ^® Cage Mixture ensures that the test run can be carried out over the entire test time and that the profile deviation remains well below the limit values. Example 3: Effect of silsesquioxane to reduce

Foaming and whitening in polyglycol-based gear oil

Reference Oil 3: Gear Oil Polyglycol, Reference Oil 3 + 5.8% Additive Package (Corrosion, PEGPOSS® Cage Oxidation Stability, Load Capacity, Mixture

Wear, foam) ISO VG 100

101 102

Viscosity 40 ° C [mm ² / sec]

AST foam test

RT 10 ml / 0:15 min 0 ml / 0: 0 min

94 ° C 20 ml / 0:15 min 10 ml / 0: 0 min

10 ml / 0.03 min

RT 20 ml / 0:25 min

Flender foam test

Foam after 1 min life

20 0

(%)

Foam after 5 min life

19 4

(%)

FZG Graying Dust Test, C / 8,3 / 90 ° C splash lubrication

Step test, change weight

17 1

(mg) after power level 10

Step test, gray spot area

10 0

(%) after power level 10

Step test,

Profilformabweichung (μιτι) after 5 4.6

Power level 10

Endurance test, change weight

1 1 8

(mg) after power level 10/400 h

Endurance test, greyish area

20 0

(%) after power level 10/400 h

Duration test, profile shape deviation

9.6 7

(μπ \) after power level 10/400 h By admixing PEGPOSS ^® Cage Mixture, there is no significant change in viscosity and ASTM foam test, however, there is a significant improvement in the Flender foam test and the occurrence of

Gray patches are almost completely suppressed.

Example 4: Filterability of Silsesquioxane - Containing Oils in

Comparison to S1O ₂ nanoparticles containing oils

Reference oil 4: Transmission oil Reference oil 4 +1, 3 Reference oil 4 + 0.5%

PAO ester ISO VG 46% IsooctylPOSS® Si0 ₂ nanoparticles,

Additive package primary particles 10 nm,

(Corrosion, surface with phenyl

Oxidation stability, and

Load bearing capacity, trimethylsilyl groups

Wear, foam)

Viscosity 40 ° C [mm ² / sec] 46.2 47 47.6

Flender foam test, before filtration test

Foam after 1 min life

2

(%) 2 2

Foam after 5 min life

3

(%) 0 2

Filtration test 3 μιτι filter

Pressure build-up / test duration <2.2 bar / 840 h <2.2 bar / 840 h> 2.2 bar / 0 h

Filtirierbarkeit pass pass fail

Flender foam test, after filtration test 3 μπι

Foam after 1 min life

5

(%) 4 not determined

Foam after 5 min life

5

(%) 5 not determined

Filtration test 10 tm filter

not determined <2.2 bar / 760 h> 2.2 bar / 0 h

Pressure build-up / test duration

Filtirierbarkeit not determined pass fail The reference oil 4 can be easily filtered at 3 μιτι. The addition of IsooctylPOSS ^® Cage Mixture has no effect on viscosity and good filtration and foaming behavior.

By using SiO ₂ nanoparticles, which can also be used to reduce the gray stain, high pressures are required for effective filtration. The proportion of inorganic SiO _x is approximately the same for the two oils with the silicon-containing aggregates.

Even with a coarser filter with 10 μπι it is not possible to filter the SiO ₂ -containing oil at low pressures, it immediately builds up a pressure of more than 2.2 bar, the test is terminated. The oil IsooctylPOSS ^® Cage Mixture containing other hand, can be filtered easily.

Example 5: Effect of silsesquioxane to reduce wear in water-based gear oil

Reference oil 5: water-based reference oil 5 + 1

Gear oil based on polyglycol (approx wt.% PEGPOSS ^® 39 wt.%) Additive package (approximately 21 Cage Mixture

Weight% corrosion, load capacity /

Wear, foam, biocide),

Water (about 40% by weight)

ISO VG 460 ISO VG 460

Viscosity 40 ° C

FZG DIN ISO 14635-3-A / 2.8 / 50 splash lubrication

Achieved power level 12 12

Total wear after

188 mg 96 mg

Force level 11

Total wear after

231 mg 145 mg

Power level 12

Additional wear after

63 mg 7 mg

Power level 10/50 h By mixing PEGPOSS ^® Cage Mixture No significant change is regarding. Viscosity, however, results in a significant improvement in the wear behavior in gear applications, especially at moderate load (power level 10).

Claims

claims

A lubricant composition for application to the surface of driving elements, the lubricant composition containing a base oil and a silsesquioxane.

Lubricant composition according to claim 1, characterized

characterized in that the silsesquioxane is the chemical formula

[RSiO3 / 2] _n has: n = 6, 8, 10, 12; where R is independent

each other = alkyl (C1-C20), cycloalkyl (C3-C20), alkenyl (C2-C20), cycloalkenyl (C5-C20), alkynyl (C2-C20), cycloalkynyl (C5-C20), Aryl (C6-C18) or heteroaryl group, oxy, hydroxy, alkoxy (C4-C10), oxirane polymer (degree of polymerization with 4 to 20

Lubricant composition according to claim 2, characterized

in that R independently of one another = hydroxyl, alkyl (C4-C10), aryl (C6-C12), in particular phenyl and tolyl, alkoxyi (C4-C10), alkenyl (C2-C10), oxirane polymer, in particular polyethylene glycol, polypropylene glycol , Polybutylenglykol and / or their copolymers (degree of polymerization with 4 to 20, especially 10 to 15

Repeating units), epoxy (C2-C10) and / or cycloalkyl (C5-C10). Lubricant composition according to claim 2 or 3, characterized in that R independently = hydroxy, alkyl (C4-C10), phenyl, tolyl, alkoxyl (C4-C10), alkenyl (C2-C10) and / or oxirane polymer, in particular polyethylene glycol , Polypropylene glycol and / or copolymers thereof (degree of polymerization with 4 to 20, in particular 10 to 15 repeating units).

5, lubricant composition according to one or more of

preceding claims, characterized in that the Siiasesquioxan the chemical formula [RSiO _{3 2} ] n (R ₂ iO) ₃ , with: n = 2, 4, 6, 8, wherein R independently = alkyl (C1-C20) - .

Cycloalkyl (C3-C20), alkenyl (C2-C20), cycloalkenyl (C5-C20), alkynyl (C2-C20), cycloalkynyl (C5-C20), aryl (C6-C18) - or

Heteroaryl group, oxy, hydroxy, alkoxy (C4-C10), oxirane polymer (degree of polymerization with 4 to 20 repeating units), carboxy, silyl, alkylsilyl, alkoxysilyl, siloxy, alkylsiloxy, alkoxysiloxy, Silylalkyl, alkoxysilylalkyl, alkylsilylalkyl, halogen, epoxy (C2-C20), ester, arylether, fluoroalkyl, blocked isocyanate, acrylate, methacrylate, mercapto, nitrile, amine, and or phosphine group, each substituted or unsubstituted.

6. lubricant composition according to one or more of

preceding claims, characterized in that the Siiasesquioxan a Siiasesquioxan according to the formula:

(I)

where R independently of one another = oxirane polymer, preferably polyethylene glycol, polypropylene glycol, polybutylene glycol and / or copolymers thereof (degree of polymerization having 4 to 20, preferably 10 to 15 repeating units) and in particular

-CH2CH2 (OCH ₂ CH 2) mOCH3, and m = 10 to 15, wherein the

Silasesquioxane optionally in the form of a mixture with other silsesquioxanes.

7. lubricant composition according to one or more of

preceding claims, characterized in that the silsesquioxane is a silsesquioxane according to the formula (I): wherein: R is independently = A! kyl (C4-C10), aryl (C6-C12), preferably isooctyl, iso-butyl and or phenyl, optionally in the form of a mixture with other silsesquioxanes.

8. lubricant composition according to one or more of

preceding claims, characterized in that the silsesquioxane is a siloxane uioxane according to the formula:

(Ii)

wherein: R independently of one another = alkyl (C4-C0) is preferably iso-octyl.

9. lubricant composition according to one or more of the preceding claims, characterized in that the Siiasesquioxan on nanoparticulate support materials, preferably on oxidic nanoparticles, in particular on amorphous silica nanoparticles present.

10. lubricant composition according to one or more of

preceding claims, characterized in that the base oil is selected from the group consisting of polyglycols, silicone oils, PFPE, mineral oils, esters, synthetic

Hydrocarbons, especially PAO, m-PAO, aromatics containing oils such as phenyl ethers, alkylated diphenyl ethers, alkylated

Naphthalene, phenyl ethers, native oils and derivatives of native oils, and mixtures thereof.

11, lubricant composition according to one or more of

preceding claims, characterized in that the

Lubricant composition contains:

5 to 80% by weight of polyalkylene glycol, preferably selected from the group consisting of randomly distributed polyoxyethylene and / or polyoxypropylene units and / or other

Polyoxyalkylenbausteinen, a block polymer of polyoxyethylene and / or polyoxypropylene units and / or others

Polyoxyalkylenbausteinen as a base oil, and / or

5 to 80% by weight of carboxylic acid ester as base oil and / or

From 2 to 80% by weight of fatty alcohol ethoxylates as base oil,

more than 10 wt% water and

0.01 to 40% by weight of Siiasesquioxan, the quantities given in each case on the total weight of

Lubricant composition are related.

12. A lubricant composition according to claim 1 1, characterized

in that the polyalkylene glycol, the carboxylic acid ester and / or the fatty alcohol ethoxylate are water-soluble.

13. lubricant composition according to one or more of

preceding claims, characterized in that the silsesquioxane in an amount of 0.01 to 40 wt.%, still

more preferably from 0.05 to 20% by weight, more preferably from 0.07 to 15% by weight and in particular from 0.1 to 10% by weight, in each case based on the total weight of the lubricant composition.

14. A lubricant composition according to one or more of

preceding claims, characterized in that polyglycol as a base oil in combination with a silsesquioxane of the formula

[RSiO _3/2 ] _n with: n = 6, 8, 10, 12, where R independently of one another = oxirane polymer, in particular polyethylene glycol, polypropylene glycol, and / or copolymers thereof (degree of polymerization with 4 to 20, in particular 10 to 15 repeat units ) is included.

15. lubricant composition according to one or more of

preceding claims, characterized in that esters, hydrocarbons, alkylated diphenyl ethers as a base oil in combination with a silsesquioxane according to the formula [RSiO3 / 2] _n with n = 6, 8, 10, 12; wherein: R independently of one another = alkyl (C1 to C20) -, or aryl (C6-C8) -, more preferably iso-octyl, iso-butyl and / or phenyl.

16. A lubricant composition according to one or more of the preceding claims, characterized in that

Silasesquioxane in an amount of 0.01 to 40 wt.%, Still

more preferably from 0.05 to 20% by weight, more preferably from 0.07 to 15% by weight, and especially from 0.1 to 10% by weight; Base oil in an amount of 99.99 to 50% by weight, more preferably 99 to 50% by weight, still more preferably 99 to 60% by weight, and especially 98 to 65% by weight; Thickener in an amount of from 3 to 40% by weight, preferably from 5 to 40% by weight, and in particular from 7 to 25% by weight; and solid lubricants in an amount of from 0% to 30% by weight, more preferably from 0 to 20% by weight; and additives are contained in an amount of from 0% by weight to 15% by weight, more preferably from 0 to 10% by weight and especially from 2 to 10% by weight, based in each case on the total weight of the lubricant composition.

17. A lubricant composition according to one or more of

preceding claims, characterized in that it is present as a gear oil formulation, and that when performing a FZG Graufleckentests C / 8.3 / 60 according to FVA information sheet 54/7 with

Injection lubrication does not exceed the profile deviation during the step run 7.5 pm and / or during endurance running 20 pm.

18. lubricant composition according to one or more of

preceding claims, characterized in that at

Performing a false brinell test using SNR FEB 2 tester at room temperature, 8000 N load, tilt angle 3 ° and 24 Hz

Oscillation frequency has a running time of at least 50 h is reached and the wear of the drive element is preferably less than 100 mg. Use of the lubricant composition according to one or more of the preceding claims for the treatment of

Surfaces of drive elements, preferably of rolling bearings, gears, plain bearings and / or chains, the drive elements preferably in plants and machinery for the production and promotion of food, in wind turbines, in automobiles, in Pulleylagern, in rail vehicles, in ships, in electric motors, generators , Ancillary components, joints present.

Use of drive elements, preferably rolling bearings, gears, plain bearings and / or chains whose surfaces with a

Lubricant composition according to one or more of

Claims 1 to 18 were treated in plants and machinery for the production and promotion of food, in wind turbines, in automobiles, in Pulleylagern, in rail vehicles, in ships, in electric motors, generators, ancillaries, joints.