EP3559176B9 - Use of calcium complex lubricating greases and calcium sulfonate complex lubricating greases for the lubrication of wire ropes - Google Patents

Description

The invention relates to the use of calcium complex grease compositions containing waxes (calcium complex hybrid greases) and/or calcium sulphonate complex grease compositions containing waxes (calcium sulphonate complex hybrid greases) as lubricants for wire ropes. Furthermore, the invention relates to a method for manufacturing the wire ropes and wire ropes provided with the grease composition.

Introduction, prior art and task

A characteristic of a lubricating grease or a lubricating grease composition is that a liquid oil component is absorbed and held by a thickener component. The pasty nature of a lubricating grease and its property of being spreadable and easily plastically deformable, together with the property of being adhesive, ensure that the lubricating grease wets the lubricating point and the lubricating effect develops permanently on the tribologically stressed surfaces.

The most important rheological properties of a lubricating grease include the consistency or its yield point, the avoidance of post-hardening and excessive oil separation under thermal and mechanical stress, and stable viscosity-temperature behavior. A thixotropic (shear-thinning) and shear-unstable behavior of the lubricating grease is often advantageous. In order to create a lubricating grease of high service value depending on the lubricating and device requirements, a high level of practical experience is required.

Lubricating greases generally consist of a thickening agent that is homogeneously distributed in a base oil. Various substances are known as base oils. Organic and inorganic compounds are used as thickeners. A variety of grease compositions are known. These also include calcium sulfonate complex greases and calcium complex greases.

The calcium sulfonate complex greases contain a base oil and a calcium sulfonate thickener which is obtained from a particulate amorphous calcium carbonate-containing overbased calcium sulfonate, the calcium carbonate converting at least partially, preferably predominantly by weight, to a calcitic structure during the course of the reaction. Such calcite-containing overbased calcium sulfonate greases are detailed, for example, in US Pat EP 0613940 B1 described.

Calcium complex lubricating greases contain a base oil and a thickener made up of calcium hydroxide, fatty acid and a complexing agent.

Wire ropes, sometimes also called steel ropes, are essential mechanical components that enable the transmission of tensile forces, especially in materials handling technology, in the fishing industry, in mining and in construction.

Wire ropes can fulfill static tasks, especially in the form of guy ropes, or are used to transmit power in dynamic applications, for example in cranes, elevators, cable cars or ski lifts. Wire ropes for dynamic applications in particular are exposed to constant alternating loads, wear out after a certain period of use and therefore have to be replaced periodically. The wear of the wire ropes is due, among other things, to the individual elements rubbing against each other. Wire ropes that are used for dynamic applications are particularly affected by frictional wear, as they are subject to constant flexing when deflecting and/or winding and unwinding.

A further optimization of the service life of wire ropes through new rope laying techniques only seems possible to a limited extent, as does the improvement of the steel quality used for the wires. The selection or creation of new lubricants and the associated extension of the service life of the tension elements has received only minor attention in recent decades. The purpose of the lubricant is to reduce frictional forces between the individual elements and/or strands of a tension element and to prevent corrosion and fretting corrosion.

At present, in addition to bitumen-based lubricants, thixotropic lubricants based on solvent raffinates are used for wire ropes, but more rarely soap greases, here predominantly lithium soap greases. An example of a wire rope lubricant containing paraffin waxes and alkali metal naphthalene sulfonate as corrosion protection is in DE1130103 B (= US3125522A ) disclosed.

In the US 2014/0182261 A2 a large number of very different greases have been proposed for wire ropes, including calcium complex greases but not calcium complex hybrid greases, calcium sulphonate complex greases or calcium sulphonate complex hybrid greases. From the examination procedure of the parallel EP2432859 it can be seen that this property right is essentially aimed at inorganic solids as a lubricant that are softer than the metal cable.

CN102827678 discloses a rope lubricating composition for reducing rust and improving lubrication.

CN103484218 discloses a wire rope lubricant.

The task of the lubricating grease to be used according to the invention is to provide the following property profile as far as possible: excellent viscosity-temperature behavior, good pumpability, a low Fraass breaking point, excellent corrosion protection even with water absorption, good elastomer compatibility, a high Dropping point, excellent anti-wear properties, good EP (extreme pressure) behavior, low oil separation, good oxidation stability, good adhesion, good pH buffering capacity, low consistency loss through water absorption and excellent shear stability (compared to thixotropic lubricants) . Also, the grease should be non-bituminous and also be available in formulations with or without a low aromatic hydrocarbon content.

Summary of the Invention

1. (i) eine Calciumsulfonat-Komplex-Hybrid-Schmierfettzusammensetzung ist enthaltend ein Basisöl, mindestens ein überbasisches Calciumsalz einer organischen Sulfonsäure, mindestens ein Komplexierunasmittel und Calciumcarbonat in calcitischer Struktur oder
2. (ii) eine Calcium-Komplex-Hybrid-Schmierfettzusammensetzung ist enthaltend ein Basisöl, mindestens eine Calciumseife zumindest einer Fettsäure einschließlich einer Hydroxyfettsäure und mindestens ein Komplexierungsmittel, oder
3. (iii) eine Mischung aus (i) und (ii) ist, wobei in der Schmierfettzusammensetzung nach (i), (ii) und (iii) -jeweils 10 bis 50 Gew.% Wachs enthalten ist und das Wachs jeweils einen Erstarrungspunkt größer 70 °C aufweist, wobei als Komplexierungsmittel zumindest Essigsäure, Dicarbonsäuren oder Phosphorsäure eingesetzt sind. und ein Herstellungsverfahren für die Drahtseile enthaltend obige Schmierfette sowie Drahtseile versehen mit der obigen Schmierstoffzusammensetzung. Die Drahtseile werden vorzugsweise für Aufzüge, Seilbahnen oder Skilifte eingesetzt.

The object is solved by the subject matter of the independent patent claims. Preferred embodiments are the subject matter of the subclaims or are described below. The invention relates to Use of a lubricating grease composition as a lubricant for wire ropes, the lubricating grease composition

1. (i) a calcium sulfonate complex hybrid grease composition containing a base oil, at least one overbased calcium salt of an organic sulfonic acid, at least one complexing agent and calcium carbonate of calcitic structure or
2. (ii) a calcium complex hybrid grease composition containing a base oil, at least one calcium soap, at least one fatty acid including a hydroxy fatty acid and at least one complexing agent, or
3. (iii) is a mixture of (i) and (ii), the lubricating grease composition according to (i), (ii) and (iii) each containing 10 to 50% by weight of wax and the wax each having a solidification point greater than 70 ° C, wherein at least acetic acid, dicarboxylic acids or phosphoric acid are used as complexing agents. and a manufacturing method for the wire ropes containing the above greases and wire ropes provided with the above lubricant composition. The wire ropes are primarily used for elevators, cable cars or ski lifts.

1. (A) ein Basisöl, z.B. zu 5-80 Gew.-%, insbesondere zu 20-55 Gew.-%;
2. (B) mindestens ein überbasisches Calciumsalz einer organischen Sulfonsäure, nachfolgend kurz Calciumsulfonat genannt, z.B. 10 bis 80 Gew.-%; in dem Calciumcarbonat zumindest teilweise, ggf. vollständig, in calcitischer Struktur vorliegt;
3. (C) ggf. eine weitere Sulfonsäure, vorzugsweise eine C12-Alkyl-Sulfonsäure, jeweils insbesondere für den Gelierungsprozess bzw. die Aktivierung,
4. (D) ggf. ein oder mehrere Aktivatoren. Dies sind z.B.:
   1. i) 1-20 Gew.-% Wasser mit anderen Alkoholen wie z.B. C1- bis C4-AI-koholen;
   2. ii) 1-20 Gew.- % C1- bis C4- Alkohole, Alkoxyalkanole und/oder Polyalkohole wie Glykole
   3. iii) 1-20 Gew.-% Wasser mit Hydroxycarbonsäuren;
   4. iv) 1-20 Gew.-% Gemische aus i) und ii) oder ii) und iii) oder i), ii) und iii), wobei die Aktivatoren während der Herstellung in der Schmierfettzusammensetzung anwesend sind und ggf. durch Hitzebehandlung zumindest teilweise ausgetrieben werden können und
5. (E) 10-50 Gew. % Wachs mit einem Erstarrungspunkt größer 70°C
6. (F) mindestens ein Komplexierungsmittel, wobei als Komplexierungsmittel zumindest Essigsäure, Dicarbonsäure oder Phosphorsäure eingesetzt sind

Für Schmierfett-Typ II: Calcium-Komplex-Hybrid-Schmierfett weist zumindest folgende Komponenten auf:

1. (a) ein Basisöl, z.B. 40-90 Gew.-%, insbesondere 60-80 Gew.-%;
2. (b) mindestens eine Calciumseife zumindest einer Fettsäure einschließlich einer Hydroxy-Fettsäure,
3. (c) mindestens ein Komplexierungsmittel, wobei als Komplexierungsmittel zumindest Essigsäure, Dicarbonsäure oder Phosphorsäure eingesetzt sind und
4. (d) 10-50 Gew. % Wachs mit einem Erstarrungspunkt größer 70°C.

The lubricating grease composition used in the wire ropes according to the invention has at least the following components:
For Type I Grease: Calcium Sulphonate Complex Hybrid Grease:

1. (A) a base oil, eg at 5-80% by weight, especially at 20-55% by weight;
2. (B) at least one overbased calcium salt of an organic sulfonic acid, hereinafter referred to as calcium sulfonate for short, eg 10 to 80% by weight; in which calcium carbonate is present at least partly, if necessary completely, in a calcitic structure;
3. (C) optionally another sulfonic acid, preferably a C12-alkyl sulfonic acid, in each case in particular for the gelation process or activation,
4. (D) optionally one or more activators. These are for example:
   1. i) 1-20% by weight of water with other alcohols such as, for example, C1 to C4-Al alcohols;
   2. ii) 1-20% by weight of C1 to C4 alcohols, alkoxyalkanols and/or polyalcohols like glycols
   3. iii) 1-20% by weight of water with hydroxycarboxylic acids;
   4. iv) 1-20% by weight of mixtures of i) and ii) or ii) and iii) or i), ii) and iii), wherein the activators are present in the grease composition during manufacture and optionally by heat treatment at least partially can be expelled and
5. (E) 10-50% by weight wax with a setting point greater than 70°C
6. (F) at least one complexing agent, at least acetic acid, dicarboxylic acid or phosphoric acid being used as complexing agent

For lubricating grease type II: Calcium complex hybrid lubricating grease has at least the following components:

1. (a) a base oil, eg 40-90% by weight, especially 60-80% by weight;
2. (b) at least one calcium soap of at least one fatty acid including a hydroxy fatty acid,
3. (c) at least one complexing agent, at least acetic acid, dicarboxylic acid or phosphoric acid being used as the complexing agent and
4. (d) 10-50% by weight wax with a setting point greater than 70°C.

• Schmierfett-Additive;
• weitere Verdicker, wie z.B.
  • andere Metallseifen von C10- bis C36-Carbonsäuren sowie deren Hydroxycarbonsäuren,
  • Salze der Phosphorsäure, Essigsäure, Borsäure und/oder eine Dicarbonsäure; und/oder
  • Polyharnstoff-Verdicker.

Both types of grease may contain the following optional components:

• grease additives;
• other thickeners, such as
  • other metal soaps of C10 to C36 carboxylic acids and their hydroxycarboxylic acids,
  • salts of phosphoric acid, acetic acid, boric acid and/or a dicarboxylic acid; and or
  • polyurea thickener.

The invention also relates to wire ropes provided with the grease composition and the manufacture of wire ropes incorporating the grease composition.

Waxes are materials that are solid and kneadable at 20°C and higher, are translucent to opaque but not glassy, melt above 40°C without decomposition, and have relatively low viscosity above the melting point.

The lubricating grease composition is also referred to below as rope lubricant.

Detailed description of the invention

The wire ropes used according to the invention can have very different configurations. They always consist of several wires which, according to a preferred embodiment, are stranded and/or twisted so that several strands form a wire rope.

For example, the wire rope can comprise a core made of steel or plastic, around which strands of 6 wires each are wound, with a further layer of wire with 12 strands, also each of 6 wires, being laid around this wire layer. The individual elements can be provided with a common casing, for example made of a plastic. In addition to the wires and strands, inserts and snaffles can also be used.

Wire ropes can, for example, have a core wire or core strand as well as an insert (also called core). Snaffles are fibers or solid polymers arranged to separate adjacent strands or wires in the same or superimposed layers, or to fill in the interstices of the rope. There are essentially three types of insole materials: fiber inlays made from natural fibers or synthetic fibers and steel inlays. Steel cores can be formed from one or more wire strands or as independently stranded wire rope. Polymer inserts can be, inter alia, solid polymer in cylindrical form with and without grooves. Wire ropes within the meaning of the present invention therefore do not necessarily consist exclusively of steel, but can also additionally include synthetic or natural materials.

Grease Type I: Calcium Sulphonate Complex Grease (Comparison Grease) and Calcium Sulphonate Complex Hybrid Grease

To prepare the calcium sulphonate complex greases , overbased calcium sulphonate is provided in a base oil. Calcium carbonate can, but does not have to be added. After thorough mixing, the activator(s) is/are added, in particular at from 40 to 100.degree. By adding the sulfonic acid, gelation occurs with a time delay, depending on the temperature. This can also be done under a slight overpressure, which increases the reaction speed. After sufficient gelation, the activator/activators are heated above the boiling point in order to remove the activator mixture. If desired, the consistency of the lubricating grease can be further thickened by additionally adding the above-mentioned further thickeners (see above under "optional components").

In order to optimize the soap structure, the soap is now heated to approx. 170-190 °C and the temperature is maintained for 30 to 60 minutes. After cooling to approx. 60 to 100 °C, additives to reduce wear, improve oxidation resistance, improve corrosion protection, etc. can be added.

The base oil (A) serves primarily as a dispersing medium, ie as a liquid carrier in which the solid particles are dispersed. The base oil is typically organic liquids that are chemically essentially inert during manufacture or intended use. The base oil preferably has a kinematic viscosity of 20 to 1000 mm ² /s, preferably 100 to 500 mm ² /s (in each case at 40° C.).

The base oil is usually an organic liquid that is non-volatile at room temperature, but which can also contain volatile components, which are usually largely separated after synthesis or refining. Volatile components are defined here as those components which boil at up to about 100° C. at atmospheric pressure, such as water or C1 to C4 alcohols. The base oil preferably has a flash point greater than 180.degree. C., in particular greater than 200.degree.

Examples of corresponding organic liquids are alkanes and cycloalkanes, aromatics and cycloaromatics, which can also be alkyl- and/or alkenyl-substituted accordingly; ethers such as dialkyl ethers; alkyl aryl ethers; cycloalkyl ethers; alkyl cycloalkyl ethers; alkanols, alkylene glycols, polyalkylene glycols and esters of these glycols; alkyl ethers of alkylene glycols and polyalkylene glycols; silicate esters, glycerides, epoxidized glycerides, aliphatic and aromatic esters; and/or slack wax (unrefined paraffin-based petroleum fractions).

Low molecular weight liquid polymers, which are generally referred to as oligomers, are also suitable as base oils. These include dimers, trimers, tetramers, pentamers, and the like. Specific examples of this large group of materials are poly-alpha-olefins defined as oligomers averaging 2 to 6 or more units of C8 to C13 alpha-olefins or independently having a viscosity of 2 to 100 mm ² /s ( at 100°C). Another important group are polyisobutylenes from 200 to 4000 g/mol (number average).

Alkyl, cycloalkyl, and aryl and alkylaryl hydrocarbons represent the preferred class of base oils from the standpoint of availability, cost, and properties. Liquid petroleum fractions represent another preferred class of base oils alkylated benzenes, naphthalenes and alkyl naphthalenes, cycloalkanes and alkylated cycloalkanes, cycloalkenes and alkylated cycloalkenes found in naphthenic-based petroleum fractions, and alkanes found in paraffin-based petroleum fractions.

Particularly preferred disperse systems are those which contain at least a certain proportion of mineral oil as a component of the disperse medium.

The term "calcium sulfonate" (B), as used herein in relation to the calcium sulfonate complex grease, generally refers to those sulfonates in which the sulfonic acid (without the metal counterion) has a molecular weight in the range of 200 to 1400 g/ mol, in particular 300 to 700 g/mol. The calcium sulfonates are generally formed in situ from a mixture of calcium oxide and/or calcium hydroxide, particularly preferably calcium hydroxide, and the sulfonic acid, preferably in solution in a volatile organic solvent, such as the above activators, and a mineral oil.

The calcium sulfonate is said to be overbased because it contains an excess of calcium carbonate and/or calcium hydroxide. The calcium hydroxide can also be provided as calcium oxide. The actual stoichiometric excess of metal can vary considerably, for example from 0.1 to about 30 or more molar equivalents, in particular greater than 0.5, so that the following TBN (Total Base Number) is established.

The overbased calcium sulphonate preferably has a TBN of from 40 to 600, more preferably from 200 to 600 as measured according to ISO 3771.

In the dispersing medium, the calcium carbonate is present as a colloidal particle. Preferably the maximum particle size is below 5000 Å. Mean particle sizes of less than 400 Å, for example in the range from 20 to 300 Å, are particularly preferred.

The other sulfonic acids (C) can be oil-soluble and, in addition, possibly also water-soluble at the same time. Preferred sulfonic acids have the following structure: The sulfonate group is attached to a cyclic or aromatic moiety, which cyclic or aromatic moiety may further have one or more linear or branched C1 to C30 hydrocarbyl moieties, preferably one or two C8 to C18 hydrocarbyl moieties remains. Examples are alkyl benzene sulfonic acids such as dobanic acid (dodecyl benzene sulfonic acid).

These sulfonic acids or sulfonates can be synthetic or natural sulfonates, the so-called "mahogany sulfonates". The term "synthetic sulfonates" refers to those sulfonates that result from the sulfonation of feedstocks that are synthetically produced. The synthetic sulfonates include alkyl sulfonates and alkyl or di-alkylaryl sulfonates. The aryl radical can be derived from benzene, toluene, phenylbenzene, diphenylbenzene, diphenylmethane, ethylbenzene, xylene isomers or naphthalene. The cyclic radical can be, for example, cyclohexane or hexahydronaphthalene.

An example of di-alkylaryl sulfonates are those with alkyl groups each having 8 to 18 carbon atoms. They are distinguished from the previous sulfonation feedstocks primarily in that they are straight chain and contain a large amount of disubstituted material.

Other sulfonates that can be used include, for example, lignin sulfonates, mono- and poly-wax substituted naphthalene sulfonates, dinonyl naphthalene sulfonates, naphthalene disulfide sulfonates, dicetyl thianthrene sulfonates, dilauryl beta-naphthol sulfonates, unsaturated paraffin wax sulfonates, hydroxy-substituted paraffin wax sulfonates, cycloaliphatic sulfonates such as lauryl cyclohexyl sulfonates, and mono- or poly-wax substituted cyclohexyl sulfonates.

The use of a mixture of water and one or more alcohols (including glycols), short chain (C1 to C4) carboxylic acids or corresponding hydroxy carboxylic acids are particular to the calcium sulfonate complex greases to convert the overbased materials from predominantly amorphous to predominantly calcitic structures effective. Such combinations often reduce the time required to carry out the process and are therefore called activators (E).

Suitable alcohols are aliphatic, cycloaliphatic and arylaliphatic mono- or polyhydroxy alcohols. Alcohols having less than about 12 carbon atoms are particularly useful. For reasons of economy and to ensure expedient operation of the process, lower alkanols, for example alkanols having fewer than 8 carbon atoms, are preferred. Examples are alkanols such as methanol, ethanol, isopropanol, n-propanol, isobutanol, tert-butanol, n-pentanol and the like; cycloalkyl alcohols such as cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 2-cyclohexylethanol and cyclopentylmethanol; phenylaliphatic alkanols such as benzyl alcohol, 2-phenylethanol and cinnamyl alcohol; Alkylene glycols with up to about 6 carbon atoms and their mono-, di- or tri-C1 to C6-alkyl ethers, such as ethylene glycol monomethyl ether, diethylene glycol, ethylene glycol, trimethylene glycol, hexamethylene glycol, triethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol, butyl glycol, butyl diglycol, butyl triglycol, and pentaerythritol.

A particularly effective combination consists of a mixture of one or more activators and water in a weight ratio of activator(s) to water of from about 1:0.05: to 1:24, preferably from 1:2 to 1:6 at least one lower alkanol or glycol present in the alcohol component of these water-alkanol mixtures.

It is particularly advantageous to use small amounts of a volatile activator, e.g. B. water or a water-soluble or slightly water-miscible or water-dispersible aliphatic C1 to C4 alcohol, preferably isopropanol, and / or a water-soluble or slightly water-miscible or easily water-dispersible alkoxyalkanol or glycols (especially mono-, di- or triglycols) , Each having 2 to 20 carbon atoms, including their mono-C1 to C4 alkyl ethers, and mixtures of one or more of these activators.

Type II grease: Calcium complex hybrid grease

Calcium Complex Hybrid Greases are usually prepared by adding base oil, fatty acid (including hydroxy fatty acids) and/or triglyceride to a container and heating to about 80°C until all components have melted.

Then Ca(OH) ₂ and optionally water are added. Furthermore, complexing agents are added. The temperature is increased to 100 °C to start the reaction. After the water of reaction has been driven off, the reaction mixture is heated further, for example to a maximum of 270.degree. After cooling down to approx. 60 to 100 °C, the lubricant additives are added to reduce wear, improve oxidation resistance, improve corrosion protection, etc.

The base oil (a) can be specified as described above for base oil (A).

The calcium soap is a calcium salt of one or more saturated or unsaturated monocarboxylic acids having 10 to 36 carbon atoms, optionally substituted, in particular having 12 to 22 carbon atoms, particularly preferably corresponding hydroxycarboxylic acids. Examples of suitable carboxylic acids are lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid, and preferably 12-hydroxystearic acid. Instead of the free acid group, corresponding lower alcohol esters can also be used with saponification, e.g. B. corresponding triglycerides and the methyl, ethyl, propyl, isopropyl or sec-butyl esters of the acid / hydroxy acid to achieve better dispersion.

At least one of acetic acid, dicarboxylic acids or phosphoric acid is used as a complexing agent within the meaning of the invention. In addition, other complexing agents can be used. Further examples of complexing agents (c) are C1 to C6 carboxylic acids, C6 to C12 di- and/or tricarboxylic acids, benzoic acid, boric acids and their salts, phosphoric acids and their salts, especially calcium salts but also lithium, sodium or potassium salts . Mixtures of 2 or more of these components are also suitable. Particularly suitable complexing agents are explained below.

The lower aliphatic carboxylic acids are C1 to C6 carboxylic acids. Examples of this class of acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, isobutyric acid, caprylic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and the like. Formic acid, acetic acid and propionic acid are preferred, with acetic acid and propionic acid being particularly suitable. The anhydrides of these acids are also suitable, so that according to the invention the term acid encompasses both the acid as such and its anhydride.

Hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gammaresorcylic acid) or 4-hydroxy-4-methoxybenzoic acid are also suitable. Particularly suitable dicarboxylic acids are adipic acid (C ₆ H ₁₀ O ₄ ), sebacic acid (C ₁₀ H ₁₈ O ₄ ), azelaic acid (C ₉ H ₁₆ O ₄ ) and/or 3- tert -butyladipic acid (C ₁₀ H ₁₈ O ₄ ).

Boric acid or boronic acids are also suitable complexing agents. These include boronic acids such as alkyl-B(OH) ₂ ; or aryl-B(OH) ₂ , boric acid (ie H ₃ BO ₃ ), tetraboric acid, metaboric acid and esters of these boric or boronic acids. Metaborate, diborate, tetraborate or orthoborate, such as calcium orthoborate or lithium tetraborate, for example, can be used as the borate.

• phosphonsäuren und -phosphonige Säuren. Phosphorsäuren, die durch Umsetzung von niederen Alkanolen oder ungesättigten Kohlenwasserstoffen, wie Polyisobutenen, mit Phosphoroxiden und Phosphorsulfiden, wie P₂O₅; und P₂S₅, hergestellt worden sind, sind besonders geeignet. Als Phosphate kommen Alkali- (bevorzugt Lithium-) sowie Erdalkali- (bevorzugt Calcium-) dihydrogenphosphat,
• hydrogenphosphat, oder -pyrophosphat in Frage.

Phosphoric acids and their salts are also suitable complexing agents. These include various alkyl and aryl phosphinic acids, -phosphinous acids,

• phosphonic and phosphonic acids. Phosphoric acids obtained by reacting lower alkanols or unsaturated hydrocarbons, such as polyisobutenes, with phosphorus oxides and phosphorus sulfides, such as P ₂ O ₅ ; and P ₂ S ₅ , are particularly useful. Alkaline (preferably lithium) and alkaline earth (preferably calcium) dihydrogen phosphate are used as phosphates,
• hydrogen phosphate or pyrophosphate in question.

• das Calciumsalz einer gesättigten oder ungesättigten Mono-Carbonsäure oder auch Hydroxycarbonsäuren mit 2 bis 8, insbesondere 2 bis 4 Kohlenstoffatomen oder einer Di-Carbonsäure mit 2 bis 16, insbesondere 2 bis 12 Kohlenstoffatomen, jeweils ggf. substituiert, und/oder
• das Calcium- oder Lithiumsalz der Borsäure und/oder das Natrium- oder Calciumsalz der Phosphorsäure und/oder
• Essigsäure oder deren Salze wie z.B. Calciumacetat.

Complexing agents are therefore, for example:

• the calcium salt of a saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids with 2 to 8, in particular 2 to 4 carbon atoms or a dicarboxylic acid with 2 to 16, in particular 2 to 12 carbon atoms, each optionally substituted, and/or
• the calcium or lithium salt of boric acid and/or the sodium or calcium salt of phosphoric acid and/or
• Acetic acid or its salts such as calcium acetate.

The wax can be added during or after the soap(s) are made. Optionally, bentonites such as montmorillonite (the sodium ions of which may have been exchanged or partially exchanged for ammonium ions), aluminosilicates, alumina, silicic acid (eg Aerosil) or di- and polyureas can also be used as co-thickeners.

The bentonites, aluminosilicates, clays, silicic acid and/or oil-soluble polymers can be added to produce the base fat or, in particular, can be added later as an additive in the second step. The di- and polyureas can be added as an additive.

The other components mentioned below can be added both to the calcium sulfonate complex hybrid lubricating grease and to the calcium complex hybrid lubricating grease.

C10 to C36 carboxylic acids and their hydroxycarboxylic acids and their esters (e.g. with methanol or glycerol as mono-, di- or triglyceride) can be used as further thickeners.

The rope lubricants for use according to the invention contain waxes. These are referred to herein as hybrid lubricants. The waxes are in particular hydrocarbon waxes such as paraffin waxes, isoparaffin waxes (microwaxes), polyolefin waxes such as PE waxes or PP waxes, FT waxes, GTL waxes, etc., candeli-ila wax, ozokerite, or polyamide waxes. Another group of waxes are ester-based waxes such as carnauba wax, candelilla wax, montan wax or alcohol-based waxes such as sonic acid wax.

The group of natural waxes includes ozokerite and montan wax (fossil wax), candelilla wax and carnauba wax (vegetable wax) or sonic acid wax (animal wax). The group of synthetic waxes includes polyamide wax (polymer wax) or GTL or FT waxes.

The waxes have a solidification point of greater than 70°C, in particular greater than 110°C or alternatively greater than 140°C (measured e.g. according to DIN ISO 2207).

The waxes are contained in the lubricating grease composition at 10 to 50% by weight, in particular 20 to 35% by weight.

It is also possible to use two or more waxes, one wax fraction having the solidification point described above and the other wax fraction having a solidification point which is at least 10° C., preferably at least 20° C., lower.

The dropping point of the lubricating grease is preferably greater than 325°C according to DIN ISO 2176.

Optionally, the compositions further contain lubricant additives as additives. Common additives are antioxidants, antiwear agents, anticorrosive agents, detergents, dyes, lubricity improvers, viscosity additives, friction modifiers and extreme pressure additives and solid lubricants.

• Antioxidationsmittel wie Amin-Verbindungen (z.B. Alkylamine oder 1-Phenylaminonaphthalin), aromatische Amine, wie z.B. Phenylnaphtylamine oder Diphenylamine, Phenol-Verbindungen (z.B. 2,6-Di-tert-butyl-4-methylphenol), Sulfurantioxidantien;
• Hochdruckadditive wie organische Chlor-, Schwefel- und/oder PhosphorVerbindungen oder organische Bismuthverbindungen;
• adhäsiv-wirkende Wirkstoffe wie C2- bis C6- Polyole, Polyglykole, Fettsäuren, Fettsäureester oder tierische oder pflanzliche Öle;
• Antikorrosionsmittel wie z.B. Petroleumsulfonat, Dinonylnaphtalinsulfonat, Sorbitanester, Sarkosine, Succinimide, Fettsäurederivate oder Imidazoline,
• Metalldeaktivatoren wie z.B. Benzotriazol und deren Derivate, Mercapto-thiadiazole oder Natriumnitrit;
• Viskositätsverbessererwie z.B. Polymethacrylat, Polyisobutylen, Poly-alpha-Olefine wie oligo-dec-1-ene, Oligocopolymere (Ethylen- und Propylencopolymerisate) und Polystyrole;
• Verschleißschutzadditive und Reibungsminderer wie Mo-Verbindungen wie Organomolybdänkomplexe (OMC), Molybdän-di-alkyl-dithiophosphate, Molybdän-di-alkyl-dithiocarbamate oder Molybdänsulfid-di-alkyl-dithiocarbamate, insbesondere Molybdän-di-n-butyldithiocarbamat und Molybdändisulfid-di-alkyldithiocarbamat (Mo₂O_mS_n(dialkylcarbamat)₂ mit m = 0 bis 3 und n = 4 bis 1), Metall-(wie Zink-) oder Ammoniumdithiocarbamat; Metall-(wie Zink-) Ammoniumdithiophosphat;
• Reibungsminderer wie z.B. funktionelle Polymere wie z.B. Oleylamide, organische Verbindungen auf Polyether- und Amidbasis, z.B. Alkylpolyethylenglykoltetradecylenglykolether, Alkyl- und/oder Aryl-Phosphorsäureester, -Phosphonsäureester und -Thiophosphorsäureester;
• Licht- und UV-Schutz-Additive.

Examples of lubricant additives are:

• antioxidants such as amine compounds (eg, alkylamines or 1-phenylaminonaphthalene), aromatic amines such as phenylnaphthylamines or diphenylamines, phenolic compounds (eg, 2,6-di-tert-butyl-4-methylphenol), sulfur antioxidants;
• extreme pressure additives such as organic chlorine, sulfur and/or phosphorus compounds or organic bismuth compounds;
• adhesive active ingredients such as C2 to C6 polyols, polyglycols, fatty acids, fatty acid esters or animal or vegetable oils;
• Anti-corrosion agents such as petroleum sulfonate, dinonylnaphthalene sulfonate, sorbitan esters, sarcosines, succinimides, fatty acid derivatives or imidazolines,
• Metal deactivators such as benzotriazole and derivatives thereof, mercapto-thiadiazole or sodium nitrite;
• Viscosity improvers such as polymethacrylate, polyisobutylene, poly-alpha-olefins such as oligo-dec-1-enes, oligocopolymers (ethylene and propylene copolymers) and polystyrenes;
• Anti-wear additives and friction reducers such as Mo compounds such as organomolybdenum complexes (OMC), molybdenum dialkyl dithiophosphates, molybdenum dialkyl dithiocarbamates or molybdenum sulfide dialkyl dithiocarbamates, in particular molybdenum di-n-butyldithiocarbamate and molybdenum disulfide di alkyldithiocarbamate (Mo ₂ O _m S _n (dialkylcarbamate) ₂ with m = 0 to 3 and n = 4 to 1), metal (such as zinc) or ammonium dithiocarbamate; metal (such as zinc) ammonium dithiophosphate;
• Friction reducers such as functional polymers such as oleylamides, organic compounds based on polyethers and amides, for example alkyl polyethylene glycol tetradecylene glycol ethers, alkyl and/or aryl phosphoric esters, phosphonic esters and thiophosphoric esters;
• Light and UV protection additives.

In addition, the grease compositions may contain conventional anti-corrosion, anti-oxidant, anti-metallic lubricant additives that act as chelate compounds, free-radical scavengers, UV protectants, reaction layer formers, and the like.

Examples of solid lubricants that can be used are polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth and zinc, salts of alkali and alkaline earth metals such as calcium carbonate, Sodium and calcium phosphates are used. Solid lubricants can be divided into the following groups: compounds with a layered lattice structure, such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride and some metal halides; oxidic and hydroxy compounds of transition and alkaline earth metals or their carbonates or phosphates; soft metals and/or plastics. The desired advantageous lubricating properties can also be set through the use of lignin sulfonates without having to use solid lubricants. In many cases, these can be dispensed with entirely or they can at least be significantly minimized.

The rope lubricant based on calcium complex hybrid soaps contains at least the following components: Areas in wt% base oil 40 to 80 Ca complex soap 5 to 55, preferably 10 to 50 (Ca soap plus complexing agent) or 5 to 30, preferably 10 to 20 Additives (optional) 0 to 20, preferably 0.5 to 10 waxes 10 to 50, preferably 10 to 35, in particular 20 to 35

Furthermore, the compositions contain at least acetic acid, dicarboxylic acid or phosphoric acid as complexing agent. The numerical values each add up to 100% by weight.

The rope lubricant based on calcium sulphonate complex hybrid soaps includes at least the following components: Areas in wt% base oil 5 to 60, preferably 20 to 40 Ca sulphonate complex soap 10 to 80, preferably 20 to 70 or 10 to 33, preferably 20 to 30 (e.g. if other thickeners are used) Additives (optional) 0 to 20, preferably 0.5 to 10 waxes 10 to 50, preferably 10 to 35 ins particularly preferably 20 to 35 Activators (usually expelled or converted in the course of the reaction) at least greater than 1, preferably greater than 2, in particular 1 to 20 or 2 to 10. further thickeners (optional) eg single or complex soaps of Ca, Li or Al. 0 to 40, preferably 2 to 20

Furthermore, the compositions contain at least acetic acid, dicarboxylic acid or phosphoric acid as complexing agent.

The numerical values each add up to 100% by weight. A special feature of the rope lubricants used according to the invention is their light appearance, since bitumen or black solid lubricants do not necessarily have to be used in order to achieve the required properties.

Typical methods for applying the rope lubricants to the wires are spraying (as an aerosol, airless or electrostatically), brushing, spraying, dip coating, flow coating, roller application, powder coating and the like. The consistency of the composition can be adjusted for the particular application method.

To produce the wire rope from a plurality of wires, the rope lubricant used according to the invention is preferably applied to the elements before the wires and/or strands are joined together. The rope lubricant can also be used for relubrication.

The individual tensile elements are preferably moved past a stationary spraying device. As a result, even very long individual elements with high tensile strength can easily be provided with a lubricating grease composition when space is limited. The tensile elements, e.g. B. metal wires, for example, can be continuously unwound from a roll, past the stationary spraying device and then formed into a flexible and deflectable pulling element, which in turn is wound onto a take-up roll.

The rope lubricants can, if necessary after dilution or in diluted form or by heating, also be used to saturate the cores of the ropes, e.g. rope cores made of sisal rope and inserting them into the rope lubricant. The wire core is then also used for relubrication from an internal reservoir.

experimental part A Used rope lubricant - commercial products and products according to the invention A. 1 rope lubricant based on a calcium sulfonate complex soap (Ca-Sul-X) (comparative example)

Input materials: wt% Overbased Ca Sulphonate* 54 base oil 19.7 tap water 5 butyl glycol 1.3 dobanic acid 5.3 Ca(OH) ₂ 2.8 12-Hydroxy Stearic Acid 3.65 Acetic acid (60% by weight) 0.6 Phosphoric acid (75% by weight) 2.75 CaCO ₃ 4.9 * Ca sulphonate with TBN 400, sales product: Calcinate ^® OR from Chemtura

The base oil was initially introduced together with the Ca sulphonate and heated to 80.degree. Then the tap water and the butyl glycol were added with constant stirring; after thorough mixing, the dobanic acid was added with stirring (still at 80° C.). Gelation took place with a time delay. After about 1 hour, the temperature was increased to 105° C. and calcium hydroxide and then 12-hydroxystearic acid were added. After a waiting time of 15 minutes, the acetic acid was added in portions. The same was done with the phosphoric acid. It was then heated to 175-180° C. for 30 minutes and then cooled. The CaCO ₃ was added at approx. 60°C. The lubricating grease was homogenized using a three-roll mill.

A.2 Rope lubricant based on a calcium sulfonate complex soap wax hybrid (Ca-Sul-X hybrid)

To 50% by weight of the Ca-Sul-X was added 25% by weight Brightstock BS 150 and heated to 80°C in a grease kettle with stirring. The paraffin wax (25% by weight) with a solidification point of 70° C. was then added in portions. After homogeneous mixing, the mixture was cooled to about 60.degree. This was followed by homogenization using a three-roller mill.

A.3 Ca-X hybrid rope lubricant based on a calcium complex soap Example of a Ca complex soap

ingredients wt% base oil 74.08 Ca(OH) ₂ 2.82 tri-sodium phosphate 0.42 Sodium tetraborate decahydrate 0.42 calcium acetate 7.42 mixed fatty acid* 7.42 beef tallow** 7.42 *Sales product : PRIFAC 5910 by CRODA
**Sales product : beef tallow, technically from SONAC

The base oil was introduced together with the mixed fatty acid and the beef tallow and heated to 80°C. An aqueous suspension of Ca(OH) ₂ was then added. Furthermore, an aqueous solution of trisodium phosphate, sodium tetraborate decahydrate and calcium acetate was added. The temperature was then gradually increased to 250°C with a residence time of approx. 30 minutes. After cooling to approx. 60°C, the lubricating grease (Ca-X) was homogenized using a three-roller mill.

To 45% by weight of the Ca-X was added 25% by weight Brightstock BS 150 and heated to 80°C in a grease kettle with stirring. A paraffin wax with a solidification point of 70° C. was then added in portions. After homogeneous mixing, the mixture was cooled to about 60° C. and 5% by weight of anti-corrosion additive (neutral calcium sulfonate) was added. This was followed by homogenization using a three-roller mill.

The following rope lubricant based on a calcium sulphonate complex soap (consistency class NLGI 000) can be used to soak sisal cores. (comparative example) Overbased Ca Sulphonate 27% base oil 59.0% tap water 2.5% butyl glycol 0.65% dobanic acid 2.65% optional Ca(OH) ₂ 1.4% 12-Hydroxy Stearic Acid 1.8% acetic acid 0.3% phosphoric acid 1.85% CaCO ₃ 2.45%

A.4 Commercial Products Used

ANTICORIT ERC 7540 EU by FUCHS, Mannheim (ANTICORIT ERC 7540 EU is a base oil-wax-based product with additives to improve corrosion protection and reduce wear) ELASKON SK21-04 by Elaskon, Dresden (wax-based rope lubricant) ELASKON 20 BB 94 by Elaskon, Dresden (wax-based rope lubricant) NYROSTEN T55 from Nyrosten, Geldern (wax-based rope lubricant) RENOLIT LC-WP 2 from FUCHS, Mannheim, Li-/Ca-12-hydroxystearate with anti-corrosion additive RENOLIT CA-FG 50 from FUCHS, Mannheim Ca-12-hydroxystearate without anti-corrosion additive Elaskon SK-U by Elaskon, Dresden (wax-based rope lubricant) Elaskon SK-CE by Elaskon, Dresden (wax-based rope lubricant) Berucoat AK 376 von Beechem, Hagen, PTFE based aqueous paste with organic binder Macromelt Henkel, Dusseldorf Bio Grease MP 2 from INTERFLON, Roosendaal, NL, PTFE lithium soap grease with phosphorous anti-wear additive. OKS 450 from OKS special lubricants, Maisach-Gernlinden, synthetic oil with ZnDTP with Mo anti-wear additive and calcium sulfonate as anti-corrosion additive

B.1 Determination of the shear viscosity of lubricating greases using the rotational viscometer according to DIN 51810

A sufficient amount of grease was applied to a plate with a spatula without air bubbles. After merging the cone/plate measuring system, excess lubricating grease was wiped off. The shear viscosity of the grease was determined by measuring torque as a function of speed at constant temperature. Shear stress and shear rate are calculated from torque and speed. A cone/plate viscometer from Anton Paar was used, which was operated with the following parameters: temperature range 30-100° C., heating rate 1° C./min, 50 mm diameter cone, angle of the cone: 1° and shear rate 500 1 /s. ANTICORIT ERC 7540 EU, ELASKON SK 21-04, ELASKON 20 BB 94 and, as a product according to the invention, Ca-Sul-X were examined.

A significantly better viscosity-temperature behavior compared to oil-wax-based rope lubricants could be determined. The greases according to the invention show viscosity-temperature curves with the desired flat progression, cf Fig.1 .

B.2 Determination of the cone penetration according to DIN 51580 or DIN ISO 2137

The bubble-free and clear melted sample was poured into a test cylinder and cooled under prescribed conditions. At constant temperature, the sinking depth of a loaded and temperature-controlled test cone (total mass 150 g) was determined with a penetrometer during a test period of 5 s. In addition to Ca-X-Hybrid, Ca-Sul-X Hybrid and in particular Ca-Sul-X showed better consistency - temperature behavior compared to an oil-wax-based rope lubricant (Elaskon 21/04), as shown in Fig.2 evident. Here, too, it is desirable for the cone penetration values to increase as little as possible with temperature, but at least for an increase to take place only at higher temperatures. Significantly better shear stability compared to oil-wax-based rope lubricants 3 deducible. The shear stability-temperature dependency was measured according to DIN 51580 ( Fig.3 ) and according to DIN ISO 2137 ( 2 and 3 ).

B.3 Determination of the breaking point according to Fraass (DIN EN 12593)

A layer of bitumen applied to a small sheet of metal was cooled by 1 °C per minute and bent in a defined manner every 1 minute. The Fraass breaking point is the temperature in degrees °C at which the bitumen layer breaks or cracks when bent under specified test conditions. The significantly better low-temperature behavior compared to oil-wax-based rope lubricants can be seen in the table below. breaking point [°C] Ca-Sul-X -62 ANTICORIT ERC 7540 EU -40 ELASKON SK 21/04 -38 ELASKON 20BB -36 NYROSTEN T55 -20

B.4 Salt spray tests according to DIN EN ISO 9227

A cold-rolled steel test specimen measuring 15 cm x 10 cm was immersed in a solution of 30% rope lubricant and solvent and suspended from a non-metallic material (e.g. synthetic fibers, cotton threads or other insulating material) to allow the solvent to evaporate. The fixtures for the samples were also made of durable non-metallic material. 4 samples were to be placed in 4 quadrants at an angle of 20° (+/- 5°) to the vertical in the chamber. The test temperature was 35 °C, the spray volume was 1.5 (+/-0.5) ml/h and the concentration of the spray solution was 50 (+/-5) g/L NaCl

Corrosion protection behavior was comparable to that of conventional oil-wax-based rope lubricant formulations t ( h ) 30 50 125 150 220 290 310 370 460 rust ( % ) Ca-Sul-X 0 0 0 0 5 5 5 40 70 Ca-Sul-X hybrid 0 0 0 0 10 30 60 75 90 Ca-X hybrid 0 0 5 10 60 75 90 90 95 ANTICORIT ERC 7540 EU 0 0 5 10 15 30 40 50 60 Elaskon 20 BB 94 15 50 100 100 100 100 100 100 100 t ( h ) 490 550 620 650 770 rust ( % ) Ca-Sul-X 80 95 100 100 100 Ca-Sul-X hybrid 90 100 100 100 100 Ca-X hybrid 95 100 100 100 100 ANTICORIT ERC 7540 EU 70 90 100 100 100 Elaskon 20 BB 94 100 100 100 100 100

In contrast to ANTICORIT ERC 7540 EU and Ca-X-hybrid, Ca-Sul-X and Ca-Sul-X-hybrid did not contain any additional anti-corrosion additives.

B.5 Testing of lubricating greases for corrosion-inhibiting properties - SKF-Emcor method (DIN 51802)

The lubricating grease was tested with the addition of water in self-aligning ball bearings. After a specified cycle with a specific running time at a speed of 80 ^rpm without heating and loading and with a specific standstill time, the raceways of the test bearing outer rings were examined for corrosion.

A comparable and in some cases better corrosion protection behavior was observed in comparison to conventional oil-wax-based rope lubricant formulations. least water 3% NaCl solution Ca-Sul-X - 0-1 Ca-X hybrid 1 (1)-2 ANTICORIT ERC 7540 EU (0)-1 4 RENOLIT LC-WP 2 0 5 RENOLIT CA-FG 50 3 - Elaskon 20 BB 94 1 2-3 degree of corrosion meaning description 0 No corrosion unchanged 1 traces of corrosion A maximum of 3 corrosion spots, none of which have a diameter of more than 1 mm 2 Light corrosion No more than 1% of the surface is corroded, but more or larger areas of corrosion than for corrosion grade 1 3 Moderate corrosion More than 1% but not more than 5% of the surface is corroded 4 Heavy corrosion More than 5% but not more than 10% of the surface is corroded 5 Very strong corrosion Over 10% of the surface is corroded

B.6 Tribological testing in the translational oscillation test device (DIN 51834)

The test specimens installed in a test chamber of the oscillation test device and wetted with lubricant were mechanically stressed at a specified normal force with a specified test frequency and a specified vibration path. The frictional forces were continuously measured.

A significantly better load carrying capacity at higher pressures was shown for the product Ca-Sul-X in comparison to Elaskon SK21/04, Elaskon 20 BB 94 and Anticorrit ERC 7540 EU, compare 4 .

B.7 Testing of lubricants - testing in the four-ball apparatus

Determination of the welding force of consistent lubricants according to DIN 51350/4 The consistent lubricant was tested in a four-ball system, consisting of a rotating ball that slides on three equal balls under selectable test forces. The test force was gradually increased until the four-ball system welded together. Welding load according to DIN 51350/4 [N] Ca-Sul-X 6500 ANTICORIT ERC 7540 EU 1800 Elaskon SK-U 1800 Elaskon SK-CE 2600

A significantly higher load-carrying capacity was found for Ca-Sul-X.

B.8 Testing of lubricants - testing in the four-ball apparatus (determination of wear parameters for consistent lubricants according to DIN 51350 / 5)

To determine the anti-wear properties, an endurance test was carried out at a specified load and then the spherical cap diameter of the three stationary balls was measured and averaged. Wear parameter according to DIN 51350/5 1h / 300 N [mm] Ca-Sul-X 0.33 Ca-X hybrid 0.28 ANTICORIT ERC 7540 EU 0.82 Elaskon 20 BB 94 0.52

Ca-Sul-X and Ca-X-Hybrid showed good anti-wear properties compared to commercially available rope lubricant compositions.

B.9 Plate-to-plate adhesion test (in-house method)

The rope lubricant sample is applied to a plate-plate rheometer using a template and heated to 80 °C. After the temperature had been reached, the excess amount of sample was smoothed off using a spatula. After cooling to 40°C, the template was removed and the top plate moved up to the re-solidified sample of lubricant until a preset distance was reached. Then, using a preset program, the upper plate was slowly immersed in the lubricant sample before it suddenly moved out of the sample again after a preset distance between the lower and upper plate had been reached. The force required to pull the top plate out of the lubricating composition was measured. It was shown that a lubricant composition based on Ca-X hybrid and a Ca-Sul-X exhibits significantly better adhesion than conventional oil-wax-based lubricants (compare Fig.5 ). Adhesion is of particular importance for rope lubricants because the grease should be "held" in the rope.

B.10 Fatigue test on the rope (Ottotest)

A rope loop, provided with the grease to be tested, is guided over a roller system and moved over the rollers in a pendulum motion. 1.2 million rollovers were carried out under the same load. The rope is evaluated based on wire break counts, rusting and the White Paper test. The white paper test refers to a piece of paper located under the test arrangement and describes the amount or number of particles thrown off the paper. The rating scale for the White Paper Test and rusting is as follows: 0 none, 1 little, 2 little, 3 much, and 4 extremely much particulate matter or rust. lubricant wire breaks rust formation White paper test Ca-Sul-X 0 0 0 ANTICORIT ERC 7540 EU 1 1 0 Berucoat AK 376 113 3 3 Macromelt 145 4 4 Bio Grease MP 2 0 1 1 OKS 450 0 2 0

Claims (14)

1. Use of a lubricating grease composition as a lubricant for wire ropes, in which the lubricating grease composition is

   (i) a calcium sulfonate complex hybrid lubricating grease composition comprising a base oil, at least one overbased calcium salt of an organic sulfonic acid, at least one complexing agent and calcium carbonate having a calcitic structure, or

   (ii) a calcium complex hybrid lubricating grease composition comprising a base oil, at least one calcium soap of at least one fatty acid including a hydroxy fatty acid and at least one complexing agent, or

   (iii) a mixture of (i) and (ii),

   wherein the lubricating grease composition according to (i), (ii) and (iii) comprises in each case 10 to 50 weight percent wax and the wax has in each case a congealing point above 70°C measured according to DIN ISO 2207, wherein as a complexing agent at least acetic acid, dicarboxylic acids or phosphoric acid are used.
2. Use according to claim 1, wherein in each case 20 to 35 weight percent of wax with a congealing point above 70°C measured according to DIN ISO 2207 is comprised.
3. Use according to claim 1 or 2, wherein the lubricating grease composition is introduced into the wire rope during manufacture of the wire rope, preferably before multiple strands and/or wires are twisted to form the wire rope.
4. Use according to claim 1, 2 or 3, wherein the calcium sulfonate complex hybrid lubricating grease composition (i) comprises:

   (a) 5 to 55 weight percent, base oil;

   (b) 10 to 80 weight percent calcium sulfonate, with the calcium carbonate present therein at least partially in calcitic form;

   (c) a further sulfonic acid; and

   (d) 10 to 50 weight percent, in particular 20 to 35 weight percent, wax,

   and the lubricating grease composition is overbased.
5. Use according to claim 3, wherein the calcium sulfonate complex hybrid lubricating grease composition (i) comprises one or more of the following activators or these were added to the calcium sulfonate complex hybrid lubricating grease composition (i) during its production:

   i) 1 to 20 weight percent water with C1 to C4 alcohols;

   ii) 1 to 20 weight percent C1 to C4 alcohols, alkoxy alkanols and/or polyalcohols such as glycols;

   iii) 1 to 20 weight percent water with hydroxycarboxylic acids;

   iv) 1 to 20 weight percent mixtures comprised of i) and ii) or ii) and iii) or i), ii) and iii);

   and the activators are present in the lubricating grease composition during production and are preferably driven out at least partially by heat treatment.
6. Use according to claim 4, wherein the calcium salt of an organic sulfonic acid is used as an overbased calcium salt of an organic sulfonic acid comprising Ca(OH)₂ and CaCO₃, preferably predominantly with respect to the mass of CaCO₃.
7. Use according to claim 1, 2 or 3, wherein the calcium sulfonate complex hybrid lubricating grease composition (ii) comprises:

   (a) 40 to 80 weight percent, base oil;

   (b) at least one calcium soap of a fatty acid including a hydroxy fatty acid;

   (c) at least one complexing agent; and

   (d) 10 to 50 weight percent, in particular 20 to 35 weight percent, wax.
8. Use according to at least one of the preceding claims, wherein the lubricating grease composition also comprises one or more of the following components:

   - lubricating grease additives;

   - other thickeners, in particular

   other metal soaps of C12 to C36 carboxylic acids as well as their hydroxycarboxylic acids;

   conversion products of metal hydroxides with a phosphoric acid, acetic acid, boric acid or a dicarboxylic acid and/or salts thereof;

   and/or

   polyurea thickener.
9. Use according to at least one of the preceding claims, wherein the lubricating grease composition has a cone penetration value of 200 to 260, preferably 220 to 250 0.1 mm measured according to DIN ISO 2137 (at 25°C).
10. Use according to at least one of the preceding claims, wherein the calcium complex hybrid lubricating grease composition (ii) and/or the calcium sulfonate complex hybrid lubricating grease composition (i) is put into the core of the rope and the calcium complex hybrid lubricating grease composition (ii) and the calcium sulfonate complex hybrid lubricating grease composition (i) in each case have a cone penetration value of 400 to 475, preferably 420 to 460 0.1 mm measured according to DIN ISO 2137 (at 25°C).
11. A method for applying

    (i) a calcium sulfonate complex hybrid lubricating grease composition comprising a base oil, at least one overbased calcium salt of an organic sulfonic acid, at least one complexing agent and calcium carbonate in a calcitic structure, or

    (ii) a calcium complex hybrid lubricating grease composition comprising a base oil, at least one calcium soap of at least one fatty acid including a hydroxy fatty acid and at least one complexing agent, or

    (iii) a mixture of (i) and (ii),

    wherein the lubricating grease composition according to (i), (ii) and (iii) comprises in each case 10 to 50 weight percent wax, and the wax has a congealing point above 70°C measured according to DIN ISO 2207, wherein as a complexing agent at least acetic acid, dicarboxylic acids or phosphoric acid are used, as a lubricant for wire ropes by application to the wires by means of spraying, spreading, injecting, dip coating, flow coating, roller application or powder coating.
12. A method according to claim 11, wherein spraying takes place as an aerosol, airless or by electrostatic means.
13. Method according to claim 11, in which the wire rope comprises multiple wires and, prior to joining the wires and/or strands, the lubricating grease composition is applied to the elements of the wire rope.
14. A wire rope provided with

    (i) a calcium sulfonate complex hybrid lubricating grease composition comprising a base oil, at least one overbased calcium salt of an organic sulfonic acid, at least one complexing agent and calcium carbonate in a calcitic structure, or

    (ii) a calcium complex hybrid lubricating grease composition comprising a base oil, at least one calcium soap of at least one fatty acid including a hydroxy fatty acid and at least one complexing agent, or

    (iii) a mixture of (i) and (ii),

    wherein the lubricating grease composition according to (i), (ii) and (iii) comprises in each case 10 to 50 weight percent wax, and the wax has a congealing point above 70°C measured according to DIN ISO 2207, wherein as a complexing agent at least acetic acid, dicarboxylic acids or phosphoric acid are used.

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