EP3269793A1 - Lubricating composition and use - Google Patents

Abstract

The present invention provides a cold washable lubricant composition and its use for application to a metal strip as a corrosion inhibitor, washing and / or forming lubricant ready. The composition has From 50 to 90% by weight of the base fluid, 3 to 15% by weight of sulphonate-based corrosion inhibitor, 1 to 20% by weight ester component, 0.5 to 3 wt% phosphorus carrier component or 1 to 10 wt% sulfur carrier component as high pressure / antiwear additive, From 1 to 15% by weight emulsifier, 0.05 to 1% by weight of carboxylic acid component, 0.05 to 1% by weight of aminic and / or phenolic antioxidant, 0.5 to 5 wt .-% wax and / or thickener component each based on the total weight of the composition. Further, a cold washable dry lubricant composition is disclosed.

Description

The invention relates to a cold washable lubricant composition and a dry lubricant composition and their use for application on a metal strip as corrosion protection, washing and / or forming lubricant.

Lubricants in metalworking perform various tasks. In the rolling mill, rolling oils or rolling emulsions are used, which are applied to the metal strip in order to influence the friction conditions between roll and strip for an optimum rolling result. Rolled oils differ in viscosity and in the presence and concentration of additives to improve lubricity, polar and non-polar additives, depending on the metal and tool. Typical additives are high pressure (EP) additives and antiwear additives such as sulfur or phosphorus carriers as well as corrosion inhibitors, e.g. Sulfonates.

After rolling, conventionally in the steel (or aluminum) factory, a corrosion inhibitor is applied to the surface of the metal belts to prevent corrosion during storage and transportation. As a result, the adherence of the stacked or rolled up to the coil (tape rolls) metal strips is avoided. Before processing, for example, in a pressing or punching tool or in another metalworking tool this corrosion inhibitor is removed by means of a wash oil or an alkaline cleaner and applied, for example, a drawing or stamping oil, which reduces the friction during the forming of the metal strip and thus facilitates the processing and ensures improved forming results or reduces the number of defective forming products.

As a corrosion inhibitor for steel and aluminum strips or coils mostly non-water-miscible oils or waxy products, called hot melts, are used, which are also not water-miscible.

The washing, drawing, stamping or other forming oils used in the metalworking plant may be, for example, aqueous emulsions or aqueous synthetic solutions or medium to high viscosity oil formulations.

It is important for all lubricants used that they have a sufficient compatibility with the overall process. Particularly in the automotive sector, there are high requirements here in order to minimize the complexity and number of steps that follow the metalworking process while at the same time reducing the scrap, e.g. defects visible in the topcoat due to residual lubricant, as low as possible. The surfaces of the pressed parts produced from the steel or aluminum strips are cleaned, if appropriate after the assembly of pressed parts using the common joining methods, before the subsequent treatment steps such as phosphating, passivation and electrophoretic dip coating are carried out. For cleaning, aqueous alkaline cleaners are usually used, which preferably consist of a two-component system in automotive body shops: a salt framework (builder) component and a surfactant component. Cleaning is usually carried out by spraying / immersion at typical application temperatures of 50 to 60 ° C.

As an alternative to a pure anticorrosion agent, a so-called prelube can be applied in the steel or aluminum plant after the rolling to finish the rolling stock.

Prelubes are compositions that combine the properties of a corrosion protection oil with the lubricity of a drawing oil. Like the anticorrosion agents, prelubes prevent corrosion and sticking during transport and storage of the metal strip coils, but also serve as a drawing lubricant in the press shop. At Prelubes, too, it is very important, especially in the automotive sector, to have excellent compatibility with every single process, from the cold-rolled strip to the body shell. If the prelube in the production chain is compatible with every step of the process (in particular welding, gluing, etc.) up to and including painting, there is a significant reduction in the number and quantity of lubricants used in the press shop (wash oils, drawing, stamping or other forming oils) and allows the work to be performed.

DE 2 207 504 A discloses an emulsifiable lubricating or lubricating agent for cold rolling metals that can be mixed with water to form a desired lubricant emulsion. The lubricant consists of 20 to 60 wt .-% oil, 20 to 59 wt .-% of solid aliphatic monocarboxylic acids having 10 to 30 carbon atoms, 1 to 15 wt .-% alkanolamine having 2 to 5 carbon atoms, 1 to 15 wt .-% Emulsifier, 0.05 to 2 wt .-% aromatic sulfonate and 2 to 15 wt .-% monoalkyl or dialkyl phosphate having 8 to 20 carbon atoms in the alkyl group and optionally 1 to 5% by weight of liquid fatty acid having 12 to 22 carbon atoms in combination with 4 to 8% by weight of aliphatic fatty acid amide having 10 to 18 carbon atoms. To prepare the emulsion with water, a temperature of about 60 ° C, preferably between 80 and 90 ° C is required.

However, aqueous lubricant emulsions are not equally suitable as a prelube for steel and aluminum due to the lower corrosion protection.

A dry Prelube lubricant (hotmelt), which should be "cold" cleanable, is in US 5,069,806 disclosed. This lubricant, which is applied in molten form on the steel strip so that a flexible solid lubricant film is obtained after cooling, can be cleaned by an alkaline solution at a temperature of 49 to 60 ° C (120 to 140 ° F). It is based on 80 to 90% by weight of a substantially saturated, refined ester formed from an aliphatic polyhydric alcohol and a C ₂ -C ₆ carboxylic acid. Preferably, this is a hydrogenated tallow triglyceride lubricant base. Other ingredients are 4 to 14 wt .-% partially esterified vegetable oil (castor oil) as a plasticizer and 2 to 6 wt .-% surfactant containing an aromatic polyether (reaction product of a C ₁₄ -C ₂₀ aromatic alcohol with 5 to 15 moles of ethylene oxide and 10 to 20 moles of propylene oxide per mole of alcohol), stearamide alkanolamide, isostearamide alkanolamide, a mixture of an aspartic acid diester and oleic acid, imidazolines or mixtures thereof. 0.1 to 2 wt .-% of an ethylene-carboxylic acid copolymer is used as the film enhancer, optionally the lubricant may additionally contain, as corrosion inhibitor, 0.1 to 3 wt.% Of an antioxidant, preferably of the hindered phenol type.

Based on this prior art, it is an object of the present invention to provide an improved cold washable lubricant composition for application to a metal strip, which can be used as a prelube or corrosion protection, forming and / or wash oil. Cold washability is here understood to mean the removal of the lubricant with an aqueous-alkaline cleaner, for example in the cleaning bath, at room temperature or without additional heating of the cleaning bath, ie well below the temperatures of 49 to 60 ° C. customary in the prior art.

The lubricant composition should simultaneously have protection against corrosion and adhesion of the metal bands, sufficient lubricity for forming processes and compatibility with all downstream manufacturing stages. In addition, the lubricant composition after application to the metal strip to form a stable and homogeneous film, inexpensive to manufacture and disposal, easy to use and suitable for various steel and aluminum grades.

This object is achieved by a lubricant composition having the features of claim 1. Further developments are set forth in the subclaims.

Furthermore, this object is achieved by a dry lubricant composition having the features of claim 13.

Claim 14 solves the problem of providing an improved use of a lubricant composition for application to a metal strip as a corrosion protection, washing and / or forming lubricant.

The lubricant composition according to the invention in a first embodiment is intended for application to a metal strip such as a steel or aluminum strip as a corrosion protection, washing and / or forming lubricant. Advantageously, the lubricant composition of the invention can be washed off cold, so that facilities and energy and costs for heating of cleaning baths can be saved in the pretreatment of formed sheet metal parts.

• 50 bis 90 Gew.-% Basisfluid,
• 3 bis 15 Gew.-% sulfonatbasierter Korrosionsinhinbitor,
• 1 bis 20 Gew.-% Esterkomponente,
• 0,5 bis 3 Gew.-% Phoshorträgerkomponente oder 1 bis 10 Gew.-% Schwefelträgerkomponente als Hochdruck-/Antiverschleißadditiv,
• 1 bis 15 Gew.-% Emulgator,
• 0,05 bis 1 Gew.-% Carbonsäurekomponente,
• 0,05 bis 1 Gew.-% aminisches und/oder phenolisches Antioxidans,
• 0,5 bis 5 Gew.-% Wachs- und/oder Verdickerkomponente,

jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, auf.A cold washable lubricant composition according to the invention for application to a metal strip as anticorrosive, washing and / or forming lubricant has

• From 50 to 90% by weight of the base fluid,
• 3 to 15% by weight of sulphonate-based corrosion inhibitor,
• 1 to 20% by weight ester component,
• 0.5 to 3% by weight of phosphorus carrier component or 1 to 10% by weight of sulfur carrier component as high pressure / antiwear additive,
• From 1 to 15% by weight emulsifier,
• 0.05 to 1% by weight of carboxylic acid component,
• 0.05 to 1% by weight of aminic and / or phenolic antioxidant,
• 0.5 to 5% by weight of wax and / or thickener component,

each based on the total weight of the composition, on.

A lubricant with this composition can actually be cold, i.e. at temperatures well below 50 ° C, especially at room temperature with an aqueous-alkaline cleaning solution.

Preferably, the proportion of the base fluid in the lubricant composition may be 55 to 80% by weight, and more preferably 60 to 70% by weight, based on the total weight of the composition. Depending on the intended application of the lubricant composition as a scrubbing lubricant, as a rolling mill applied corrosion lubricant or prelube or as a reshaping lubricant different viscosities are provided, which are adjusted by selection and / or composition of the base fluid. In order to set a desired viscosity, therefore, a mixture of at least two base oils differing with respect to their kinematic viscosity at 40 ° C. can be used as base fluid, which consists predominantly of base oils of group I and group II with a kinematic viscosity of 40 ° C. to 700 mm ² / s are selected. However, Group III and Group IV base oils are not excluded. By selecting the different base oils in terms of their viscosity and their weight ratio to each other, the kinematic viscosity at 40 ° C of the composition can be adjusted as needed in a range of 5 to 300 mm ² / s.

The lubricant composition according to the invention can be used as a prelube lubricant, which combines corrosion protection function with emulsifiability and lubricity in machining processes. As anticorrosion lubricant, the composition according to the invention is applied in the rolling mill in order to protect the metal strip from adhering and corrosion during storage and transport. Optionally, in further processing operation, for example press shop, it may be necessary to apply a further lubricant at least selectively for forming. This forming or drawing oil lubricant may also have a composition according to the invention with adapted viscosity. Similarly, an optional wash oil may be a modified viscosity composition of the invention. For washing lubricants is a kinematic viscosity at 40 ° C in the range of 5 to 25 mm ² / s, preferably 8 to 15 mm ² / s, for rolling mill applied corrosion lubricants or prelubes 20 to 120 mm ² / s, preferably 60 to 100 mm ² / s, and for forming lubricant 60 to 300 mm ² / s, preferably 130 to 200 mm ² / s, can be adjusted.

For example, for use as a prelube, the base fluid of a particularly preferred lubricant composition may comprise a first base oil having a kinematic viscosity at 40 ° C of 700 mm ² / s and a second base oil having a kinematic viscosity at 40 ° C of 40 mm ² / s , In order to achieve a kinematic viscosity at 40 ° C of 100 ± 10 mm ² / s, a weight ratio of the first base oil to the second base oil in the base fluid is set between 3: 1 to 4: 1.

The sulfonate-based corrosion inhibitor of the lubricant composition is selected from the group comprising overbased and neutral Ca sulfonates, overbased and neutral Na sulfonates, and mixtures thereof, wherein a composition of the invention contains at least one overbased sulfonate. Preferably, the composition may contain from 0.5% to 5% by weight of overbased Na sulfonate and / or from 2% to 10% by weight of overbased Ca sulfonate. Optionally, in addition to the at least one overbased sulfonate, a composition of the invention may contain from 1 to 5 weight percent neutral Ca sulfonate and / or from 1 to 5 weight percent neutral Na sulfonate, each on condition that the weight proportions of the overbased and optionally neutral sulfonates in total from 3 to 15 wt .-% sulfonate-based corrosion inhibitors based on the total weight of the composition.

A preferred concept of sulfonate for a lubricant composition according to the invention comprises from 1 to 5% by weight of overbased Na sulfonate and from 3 to 5% by weight of overbased Ca sulfonate. More preferably, the composition may have as corrosion inhibitors 1.5 wt .-% overbased Na sulfonate and 3.5 wt .-% overbased Ca sulfonate.

An alternative concept of sulfonate provides, in addition to 1 to 5 wt.% Overbased Na sulfonate and 3 to 5 wt.% Overbased Ca sulfonate 1 to 5 wt.% Neutral Ca sulfonate. This sulfonate concept preferably comprises 1.5% by weight of overbased Na sulfonate and 3.5% by weight of overbased Ca sulfonate and 3% by weight of neutral Ca sulfonate.

Further alternative compositions have only overbased Na sulfonate with 3 to 6 wt .-%, preferably 4.6 wt .-%, or only overbased Ca sulfonate with 3 to 10 wt .-%, preferably 5.2 wt .-% , on.

The stated proportions by weight are based on the total weight of the composition.

Furthermore, a lubricant composition according to the invention may additionally comprise from 0.05 to 1.7% by weight of at least one further inhibitor component, based on the total weight of the composition. The further inhibitor component in the composition can be selected from 0.05 to 0.2 wt .-% triazoles, preferably 0.1 wt .-% benzotriazole or water-soluble benzotriazole derivatives, and / or 0.1-1.5 wt. - Amines, preferably trialkanolamines such as triethanolamine.

The ester component of a lubricant composition may be 10 to 20% by weight of fatty acid ester or 1 to 5% by weight of wool fat ester, based in each case on the total weight of the composition. Preferably, a composition of the invention may comprise 15% by weight of fatty acid ester based on the total weight of the composition.

Preferred lubricant compositions have, as high-pressure / anti-wear additives, a phosphorus component whose proportion is in particular 2% by weight, based on the total weight of the composition. The phosphorus carrier component may be a dialkyl hydrogen phosphite wherein each alkyl group is saturated or unsaturated and has 14 to 22 carbon atoms, for example, di-oleyl hydrogen phosphite.

The emulsifier which provides improved cleanability with an aqueous cleaner may be selected from nonionic surfactants, especially fatty alcohol alkoxylates. Preferred fatty alcohol ethoxylates are based on fatty alcohols having 16 to 18 carbon atoms and have a degree of alkoxylation or degree of ethoxylation of 2 to 5 mol. It is also possible to use mixtures of different nonionic surfactants or fatty alcohol alkoxylates, which differ, for example, in the degree of alkoxylation. It is also possible to use propoxylated or mixed-ethoxylated and propoxylated fatty alcohols as emulsifiers.

As alternative or additional emulsifiers it is possible to use anionic surfactants, for example alkyl ether carboxylic acids or phosphorus esters. Preferred among the alkyl ether carboxylic acids are C _14-22 fatty alcohol polyglycol ether carboxylic acids, which may be saturated or unsaturated. Suitable phosphorus esters are alkoxylated fatty alcohol phosphate esters, preferably phosphate esters of saturated or unsaturated fatty alcohols having 16 to 18 carbon atoms and a degree of ethoxylation of, for example, 5 moles. But here also phosphate esters of fatty alcohols with a different degree of ethoxylation or propoxylated or mixed propoxylated and ethoxylated fatty alcohols are conceivable.

A proportion of each emulsifier component, alone or in the mixture, is in each case from 1 to 5% by weight, based on the total weight of the composition, provided that the total content of emulsifier does not exceed 15% by weight.

A preferred composition according to the invention comprises 7.5% by weight of fatty alcohol alkoxylate mixture as emulsifier, based on the total weight of the composition, the fatty alcohol alkoxylate mixture consisting in particular of 5% by weight of C _16-18 fatty alcohol with a degree of ethoxylation of 5 mol and 2.5% by weight % _C16-18 fatty alcohol having a degree of ethoxylation of 2 moles.

The carboxylic acid component of a lubricant composition may be selected from saturated or unsaturated carboxylic acids having 16 to 22 carbon atoms, such as tall oil fatty acids, oleic acid and behenic acid, or dimer acids, which are dicarboxylic acids prepared by dimerization of tall oil unsaturated fatty acids. Also mixtures of these are conceivable. A preferred composition may comprise 0.5% by weight tall oil fatty acid based on the total weight of the composition. Tall oil fatty acids having a high fatty acid content and a low content of resin acids are preferably used.

The amine antioxidant contained in the lubricant composition of the present invention may be a reaction product of N-phenylbenzolamine with 2,4,4-trimethylpentene (Irganox® L57). The phenolic antioxidant may, for example, be octyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (Irganox® L135), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( IRGANOX® L107). A preferred composition may comprise 0.25% by weight of amine antioxidant and 0.25% by weight of phenolic antioxidant, preferably octyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, based on the total weight of the composition.

• paraffinischen Wachsen,
• Rizinusölderivaten, insbesondere auf hydriertem Rizinusöl basierende thixotrope Verdicker,
• Fettsäurederivaten, insbesondere Fettsäureester oder Fettsäureamide der C16-20 gesättigten und ungesättigten Fettsäuren, beispielsweise Methyl-12-hydroxystearat, Octadecylstearate oder raffiniertes Ölsäureamid,
• Polymeren, beispielsweise Blockpolymeren, insbesondere linearen Triblock-Copolymeren basierend auf Styrol und Ethylen/Butylen mit PS-PE/PB-PS und 30% PS, Polymethacrylaten in Mineralöl und niedermolekularen Polyisobutenen (Pib 1300), ausgewählt sein.

The wax and / or thickener component of a lubricant composition of the invention may consist of

• paraffinic waxes,
• Castor oil derivatives, in particular thixotropic thickeners based on hydrogenated castor oil,
• Fatty acid derivatives, in particular fatty acid esters or fatty acid amides of the C16-20 saturated and unsaturated fatty acids, for example methyl 12-hydroxystearate, octadecyl stearate or refined oleic acid amide,
• Polymers, for example block polymers, in particular linear triblock copolymers based on styrene and ethylene / butylene with PS-PE / PB-PS and 30% PS, polymethacrylates in mineral oil and low molecular weight polyisobutenes (Pib 1300).

A preferred composition may comprise 3% by weight paraffinic wax with solidification point at 64 to 66 ° C as wax and / or thickener component.

• 10 bis 90 Gew.-% Wachskomponente,
• 3 bis 15 Gew.-% sulfonatbasierter Korrosionsinhinbitor,
• 0,05 bis 1,7 Gew.-% zumindest einer weiteren Inhibitorkomponente,
• 0,5 bis 3 Gew.-% Phoshorträgerkomponente oder 1 bis 10 Gew.-% Schwefelträgerkomponente als Hochdruck-/Antiverschleißadditiv,
• 0 bis 15 Gew.-% Emulgator,
• 0,05 bis 1 Gew.-% Carbonsäurekomponente,
• 0,05 bis 1 Gew.-% aminisches und/oder phenolisches Antioxidans,

jeweils bezogen auf das Gesamtgewicht der Zusammensetzung.A further composition according to the invention relates to a dry lubricant, also called hotmelt, waxes being used instead of a base fluid. The hotmelt composition is heated as a corrosion protection lubricant or prelube for application to a metal strip or, if appropriate, can also be used as an aqueous dispersion, but can also be cold-cleaned in the composition according to the invention. The cold washable dry lubricant composition comprises:

• 10 to 90% by weight wax component,
• 3 to 15% by weight of sulphonate-based corrosion inhibitor,
• 0.05 to 1.7% by weight of at least one further inhibitor component,
• 0.5 to 3% by weight of phosphorus carrier component or 1 to 10% by weight of sulfur carrier component as high pressure / antiwear additive,
• 0 to 15% by weight emulsifier,
• 0.05 to 1% by weight of carboxylic acid component,
• 0.05 to 1% by weight of aminic and / or phenolic antioxidant,

each based on the total weight of the composition.

Depending on the proportion of the wax component, it may be necessary to add a base fluid to supplement the 100% by weight of the composition.

The wax component is selected from one or more organic compounds having a melting range of 35 to 75 ° C, preferably 40 to 70 ° C, and may be a polyalkylene glycol, polyalkylene glycol ester, an ester, ester ethoxylate, a carboxylic acid ethoxylate or an ether carboxylic acid or its alkali and alkaline earth metal soaps, glycerol fatty acid esters, a polyol ester or sorbitol esters or their ethoxylates, an alcohol or fatty alcohol or their ethoxylates or be.

Examples are polyethylene glycols 1500, 2000 and 4000, polyalkylene glycol esters, sorbitan tristearate, sorbitan tristearate ethoxylate, sorbitan monostearate, sorbitan monostearate ethoxylate, stearyl alcohol, stearyl cetyl alcohol, 12-hydroxy stearic acid, methyl 12- Hydroxy stearate, glycerol monostearate, glycerol monolaurate, PEG1500 monostearate, pentaerythritol tetrastearate.

Also combinations of said wax components are conceivable, e.g. Sorbitan tristearate and sorbitan tristearate ethoxylate (e.g., 40:60 ratio) or sorbitan monostearate and sorbitan monostearate ethoxylate (e.g., 75:25 ratio). But there are also other combinations of said wax components conceivable.

In the case of solid wax components or thickeners which themselves have an emulsifying action (for example the abovementioned sorbitan ethoxylates), the addition of the liquid emulsifiers may optionally be omitted.

An embodiment of the dry lubricant composition may provide that the wax component used is a mixture of 7.5% by weight of sorbitan tristearate and 7.5% by weight of sorbitan tristearate ethoxylate (20 EO), and the remaining components such as are included above, ie that the emulsifier can be omitted; Here, a base oil is added to supplement the 100% by weight of the composition.

• paraffinischen Wachsen,
• Rizinusölderivaten, insbesondere auf hydriertem Rizinusöl basierende thixotrope Verdicker,
• Fettsäurederivaten, insbesondere Fettsäureester oder Fettsäureamide der C16-20 gesättigten und ungesättigten Fettsäuren, beispielsweise Methyl-12-hydroxystearat, Octadecylstearate oder raffiniertes Ölsäureamid,

ausgewählt sein.The wax component may further be as above in the lubricant composition of the invention

• paraffinic waxes,
• Castor oil derivatives, in particular thixotropic thickeners based on hydrogenated castor oil,
• Fatty acid derivatives, in particular fatty acid esters or fatty acid amides of the C16-20 saturated and unsaturated fatty acids, for example methyl 12-hydroxystearate, octadecyl stearate or refined oleic acid amide,

be selected.

Different wax components may also be blended to impart the desired properties to the dry lubricant composition.

The further components may be formed in further developments of the dry lubricant composition according to the above information on the lubricant composition according to the invention.

In the present application, the lubricant compositions of the invention are described as anticorrosive, washing and / or forming lubricants and dry lubricant compositions as anticorrosive lubricant or Prelube. Lubricant compositions according to the invention which are used as anticorrosive agents or preload and the dry lubricant compositions are applied on the mill side, washing and forming lubricants in the press shop. Corrosion inhibitors or pretubes, washing and forming lubricants are to be understood as meaning all synonymously used terms which refer to such lubricants. Corrosion inhibitors may also be referred to, for example, as anticorrosion oil, etc., and prelubes, for example, as anticorrosive oil with reshaping properties, etc. For dry lubricants, terms such as hotmelt, hotmelt drylube, drylube or dry lubricant are also used. Washing lubricants are also referred to as wash oil or oily washing fluid, for example, and forming lubricant includes draw oil, forming lubricant, drawing lubricant, additional lubricant, etc.

A use according to the invention of the lubricant composition likewise according to the invention relates to its application on a metal strip as anticorrosive, washing and / or forming lubricant. The lubricant composition allows cold washing with an alkaline-aqueous cleaner. As for the cleaning the metal strip of the emulsifier contained in the lubricant composition according to the invention is introduced into the alkaline-aqueous cleaner, its surfactant component must be proportioned correspondingly lower; ie, the surfactant concentration of the alkaline aqueous cleaner is matched to the emulsifier content of the lubricant composition.

Other embodiments as well as some of the advantages associated with these and other embodiments will become apparent and better understood by the following detailed description.

The lubricant composition of the invention relates to the product range corrosion protection oils and forming lubricants and wash oils, especially in the automotive body shell process. This begins with the application of the anticorrosive oil or prelubes to the metal sheet in the steel or aluminum plant and ends when the primer is applied by means of cathodic dip painting (KTL). Depending on the target product, Prelube or corrosion protection oil, wash oil and drawing oil are used. Prior to the KTL, all oils are removed by an alkaline-aqueous cleaner system, which previously required a temperature of about 55 ° C.

Come as a prelube or anti-corrosion oil, wash oil and drawing oil lubricant compositions according to the invention are used, they can be completely removed even at low detergent temperatures from the plate (example: car body shop), so that costs and energy saved by the heating of detergent baths.

The emulsifiers used as cleaning-active constituents in the lubricant composition according to the invention disturb the main properties of the oils-depending on the product type, these are corrosion protection, lubricating and / or washing action-especially when using nonionic surfactants. In addition, the emulsifiers used meet the requirements for compatibility with subsequent process steps (including shell bonding, welding, cathodic dip coating).

Furthermore, the lubricant composition according to the invention fulfills the requirements with respect to the applicability in the steel or aluminum plant. One common method of application there is electrostatic spraying; but it can also be used other types of application, such as conventional spraying. Suitable compositions for this purpose have a kinematic viscosity at 40 ° C in the range of 20 to 120 mm ² / s. For spraying a slight warming to 50 to 60 ° C for complete dissolution of the contained wax / thickener may be required. For other forms of application, for example by means of roll coaters or similar coating systems, or if the composition is designed as a washing or forming or drawing oil, but the composition can also be set in a different viscosity range and eliminates heating for application. Optionally, a lubricant composition of the invention may also be applied as an aqueous dispersion. Usually, the application of forming oils by spraying, or more rarely by roller coater. For the application of wash oils, however, rather felt, squeezing and / or rubber rollers are used.

With a suitably adjusted viscosity, the composition according to the invention can be used as a uniform, thin layer as corrosion lubricant or prelube in the range from 0.5 to 2.5 μm, preferably about 1 μm, as forming lubricant in the range from 1 to 10 μm, preferably about 2 microns, and as a wash lubricant in the range of 1 to 5 microns, preferably 0.5 to 1 micron, apply to the metal strip, and does not run off due to the waxes / thickeners contained. A total thickness of the layer formed from different compositions is preferably in the range of 1 to 5 μm, more preferably about 2 μm. Thus, the composition according to the invention not only provides corrosion protection for both steel and aluminum during storage and transport but acts as a lubricant during forming. The joining processes following welding such as welding, gluing, crimping or clinching can be carried out without purification, i. with adherent lubricant composition, which is thus compatible with most or all common body building adhesives such as high strength construction adhesives or sealants.

Before the phosphating and painting, the lubricant composition is removed by means of an alkaline aqueous cleaner in the dipping / spraying bath. Complete removal is important to avoid paint defects due to lubricant residues.

By removed from the sheet metal parts to be cleaned lubricant composition enter the emulsifier contained in the lubricant composition in the cleaning bath and thus increase there the concentration of surfactants or emulsifiers, since the cleaning baths are treated and recirculated. As an increase in these components Without proper consideration in the cleaning process would lead to disturbances, the registered by the corrosion protection and processing oils emulsifier must be taken into account in the dosage of the cleaning baths by the surfactant component is metered correspondingly lower. Table 1 shows a particularly preferred lubricant composition having a kinematic viscosity at 40 ° C of 100 mm <sup> 2 </ sup> / sec: Wt .-% component example 66.4 base fluid -52.2 Group I base oil, kin. Viscosity (40 ° C) = 700 mm ² / s PIONIER® 4529 (H & R KG, Hamburg, DE) -14.2 Group II base oil, kin. Viscosity (40 ° C) = 40 mm ² / s Chevron Neutral Oil 220 R (Chevron, Ghent, Belgium) 5 Sulfonate component overbased Na sulfonate - 1.5 Lubrizol® 5318A (Lubrizol Company, Wickliffe, Ohio, USA) -3.5 overbased Ca sulfonate Calcinate ™ OR (Chemtura Corp. Petroleum Additives, Middlebury, CT, USA) 0.1 inhibitor component benzotriazole 15 Ester component of saturated fatty acid esters, 2-ethylhexyl palmitate Metalest EHP 99 (FACI Metalest, Zaragoza, Spain) / Radia 7780 (Oleon GmbH, Wiesbaden, DE) 2 Phosphorus component di-oleyl-hydrogen-phosphite Doverphos® 253 (Dover Chemical Corp., Dover, Ohio, USA) 7.5 Emulsifier nonionic surfactant, fatty alcohol ethoxylate, 5 mol Emulsogen M (Clariant, Muttenz, Switzerland) Rhodasurf CET 5 (Rhodia Novecare, Courbevoie, France) -5 -2.5 nonionic surfactant, fatty alcohol ethoxylate, 2 mol Rhodasurf CET 2 (Rhodia Novecare, Courbevoie, France) 0.5 Carboxylic acid component Tall oil fatty acid for2 (Forchem Oy, Rauma, Finland) 0.25 Amine antioxidant Irganox L57 (Ciba Specialty Chemicals, Basel, Switzerland) 0.25 phenolic antioxidant Irganox L135 (Ciba Specialty Chemicals, Basel, Switzerland) 3 Wax component paraffinic waxes, solidification point 64-66 ° C HR 64-66 (H & R KG, Hamburg, DE)

Alternative compositions vary mainly with regard to the sulfonate concept, which is used as a corrosion inhibitor. To a lesser extent, the base oil mixture that forms the base fluid can also vary to adjust the viscosity in the desired range.

While the first particularly preferred lubricant composition has only overbased Na and Ca sulfonates, an alternative composition may contain overbased and neutral sulfonates: Table 2 shows base fluid and sulfonate component of an alternative lubricant composition corresponding to other components. Wt .-% component example 63.4 base fluid - 49.2 Group I base oil, kin. Viscosity (40 ° C) = 700 mm ² / s PIONIER® 4529 (H & R KG, Hamburg, DE) -14.2 Group II base oil, kin. Viscosity (40 ° C) = 40 mm ² / s Chevron Neutral Oil 220 R (Chevron, Ghent, Belgium) 8th sulfonate - 1.5 overbased Na sulfonate Lubrizol® 5318A (Lubrizol Co., Wickliffe, Ohio, USA) - 3,5 overbased Ca sulfonate Calcinate ™ OR (Chemtura Corp. Petroleum Additives, Middlebury, CT, USA) 3 neutral Ca sulfonate Arcot 626F (PCAS, Longjumeau, France)

Tables 3 and 4 show other alternative compositions, each containing only overbased Na sulfonate or only overbased Ca sulfonate. Again, the other components correspond to those in Table 1. Table 3 Wt .-% component example 66.8 base fluid - 52.6 Group I base oil, kin. Viscosity (40 ° C) = 700 mm ² / s PIONIER® 4529 (H & R KG, Hamburg, DE) -14.2 Group II base oil, kin. Viscosity (40 ° C) = 40 mm ² / s Chevron Neutral Oil 220 R (Chevron, 9052 Ghent, Belgium) 4.6 overbased Na sulfonate Lubrizol® 5318A (Lubrizol Co., Wickliffe, Ohio, USA) Wt .-% component example 66.2 base fluid - 52 Group I base oil, kin. Viscosity (40 ° C) = 700 mm ² / s PIONIER® 4529 (H & R KG, Hamburg, DE) -14.2 Group II base oil, kin. Viscosity (40 ° C) = 40 mm ² / s Chevron Neutral Oil 220 R (Chevron, Ghent, Belgium) 5.2 overbased Ca sulfonate Calcinate ™ OR (Chemtura Corp. Petroleum Additives, Middlebury, CT, USA)

It is emphasized that the composition of the invention should not be limited to the particularly preferred compositions exemplified herein.

It will be apparent to those skilled in the art that the composition can be changed within the claimed limits to modify certain properties of the composition. Also, alternatives to the mentioned components and examples within the scope are readily conceivable.

Thus, instead of the two base oils listed in Tables 1 to 4, which form the base fluid, other Group I and Group II oils are also considered, which may have different kinematic viscosities - especially if the kinematic viscosity (40 ° C) of the composition deviating from the above 100 mm ² / s within the claimed range of 8 to 200 mm ² / s to be set. Table 5 indicates further base oils which can be used in a composition according to the invention for forming the base fluid having the desired viscosity: base oil kinematic viscosity (40 ° C) example naphthenic kV40 = 7.6 mm ² / s NS 8 (Nynas, Stockholm, Sweden) naphthenic kV40 = 8 mm ² / s T9 (Nynas, Stockholm, Sweden) / GADUS NH 8/40 (Shell, The Hague, Netherlands) Group I kV40 = 114 mm ² / s SN 600 (Shamrock, Limassol, Cyprus) Group I kV40 = 500 mm ² / s BRIGHTSTOCK 460 (Total Lubrifiants, LeHavre, France) Group II kV40 = 102 mm ² / s CHEVRON NEUTRAL 600 R (Chevron, Ghent, Belgium) Group II kV40 = 3.5 mm ² / s Base Oil PL 35 (Petro Canada, Calgary / Canada)

Concerning the sulfonate component, the overbased Ca sulfonate may also be Calcinate ™ OTS (Chemtura Corp. Petroleum Additives, Middlebury, CT, USA). As a neutral Na sulfonate example Petronate® H (Sonneborn, Amsterdam, Netherlands) in question.

Apart from benzotriazole, water-soluble benzene derivatives, for example Irgamet 42 (Ciba Spezialitätenchemie, Basel, Switzerland), or triethanolamine in the claimed limits can be used as the inhibitor component. Table 6 indicates further, alternatively suitable ester components: Fatty acid ester FS ester saturated, TMP, branched PRIOLUBE 1968 (Croda, Nettetal, DE) Fatty acid ester FS ester saturated, TMP C8-10 PRIOLUBE ™ 3970 (Croda, Nettetal, DE) Fatty acid ester NPG diisostearate PRIOLUBE ™ 1973 (Croda, Nettetal, DE) Fatty acid ester TMPO RADIALUBE 7364 (Oleon GmbH, Wiesbaden, DE) Fatty acid ester Triglyceride C8-C10 RADIAMULS MCT 2106 (Oleon GmbH, Wiesbaden, DE) Fatty acid ester HC, butyl ester Alphanox 2015 (alpha Chemie, Freital, DE) Wollfettester Wool fat ester (PE) Ewasol EPS 24 (H. Erhard Wagner GmbH, Bremen, DE) Wollfettester Wollfettester Ewasol LY10 (H. Erhard Wagner GmbH, Bremen, DE) phosphor carrier Oleyl alcohol ethoxylate phosphate Rhodafac PA 35 (Rhodia Novecare, Courbevoie, France) phosphor carrier Dimethyloctadecenylphosphonat Duraphos 100 (Rhodia Novecare, Courbevoie, France) phosphor carrier triaryl Irgalube TPPT (Ciba Specialty Chemicals, Basel, Switzerland) sulfur carriers sulphurised hydrocarbon TPS® 20 (Arkema Inc., King of Prussia, Pennsylvania, USA) sulfur carriers Sulfur polymer from lard oil Additin RC 8000 (Rhein-Chemie Additives, Mannheim, DE) sulfur carriers overbased Na thiophosphonate Roscan 491 (PCAS, Longjumeau, France) sulfur carriers S-ester Additin RC 2415 (Rhein-Chemie Additives, Mannheim, DE) sulfur carriers S-ester (oleic acid methyl ester) Additin RC 2411 (Rhein-Chemie Additives, Mannheim, DE) sulfur carriers Amindialkyldithiophosphat Additin RC 3880 (Rhein-Chemie Additives, Mannheim, DE) sulfur carriers Ethylhexyl-Zn-dithiophosphate Additin RC 3080 (Rhein-Chemie Additives, Mannheim, DE)

Besides the preferred nonionic surfactants, anionic surfactants such as alkyl-ether carboxylic acid, e.g. Akypo RCP 105 (Kao Chemicals Europe, Barcelona, Spain), or phosphate esters such as Rhodafac PA 35 (Rhodia Novecare, Courbevoie, France).

Also suitable as carboxylic acids are pure oleic acid, dimer acid (for example Pripol 1022, (Croda, Nettetal, DE)) or behenic acid (Prifrac 2989 (Croda, Nettetal, DE)).

Alternative phenolic antioxidants are e.g. Butylhydroxytoluene or Irganox® L 107 (BASF, Ludwigshafen, DE).

Alternative waxes or thickeners for adjusting the viscosity / rheology of the composition can be selected from Table 8: paraffinic waxes Solidification point 63 ° C Sasolwax 6072 Sasol, Hamburg, DE) castor oil castor oil LUVOTIX R (Lehmann & Voss & Co. KG, Hamburg, DE) castor oil hydrogenated castor oil derivative, micronised Albothix 82-32 (Alberdingk Boley GmbH, Krefeld, DE) Fatty acids and derivatives Methyl 12-hydroxystearate NORACID 1115 (Nordmann Rassmann GmbH, Hamburg, DE) Fatty acids and derivatives Octadecyl stearate, stearyl stearate fatty acid amide Refined oleic acid amides Crodamide OR (Croda, Nettetal, DE) block polymer PS-PE / PB-PS (30% PS) type ABA KRATON® G1650 EU (Kraton Polymers, Frankfurt aM, DE) PMA Polymethacrylate in mineral oil Viscoplex® 1-360 (Evonik, Essen, DE) PIB Polyisobutylene 1300

Claims (15)

Cold washable lubricant composition for application on a metal strip as anticorrosive, washing and / or forming lubricant,
characterized in that
the composition From 50 to 90% by weight of the base fluid, 3 to 15% by weight of sulphonate-based corrosion inhibitor, 1 to 20% by weight ester component, 0.5 to 3 wt% phosphorus carrier component or 1 to 10 wt% sulfur carrier component as high pressure / antiwear additive, From 1 to 15% by weight emulsifier, 0.05 to 1% by weight of carboxylic acid component, 0.05 to 1% by weight of aminic and / or phenolic antioxidant, 0.5 to 5 wt .-% wax and / or thickener component each based on the total weight of the composition. Lubricant composition according to claim 1,
characterized in that
the composition
55 to 80 wt .-%, particularly preferably 60 to 70 wt .-% base fluid based on the total weight of the composition, wherein by selection and / or composition of the base fluid. the kinematic viscosity at 40 ° C of the composition in a range of 5 to 300 mm ² / s is adjustable, wherein the kinematic viscosity at 40 ° C for scrubbing lubricant in the range of 5 to 25 mm ² / s, preferably 8 to 15 mm ² / s, for rolling mill applied corrosion lubricants or prelubes 20 to 120 mm ² / s, preferably 60 to 100 mm ² / s, and for forming lubricant 60 to 300 mm ² / s, preferably 130 to 200 mm ² / s, is set. A lubricant composition according to claim 1 or 2,
characterized in that
the base fluid is a mixture of at least two base oils differing in kinematic viscosity at 40 ° C selected from Group I and Group II base oils having a kinematic viscosity at 40 ° C of 3 to 700 mm ² / s, wherein an anticorrosive lubricant preferably the base fluid has a first base oil with a kinematic viscosity at 40 ° C of 700 mm ² / s and a second base oil with a kinematic viscosity at 40 ° C of 40 mm ² / s, more preferably a weight ratio of the first base oil to the second base oil in the base fluid is 3: 1 to 4: 1 and the kinematic viscosity at 40 ° C is 100 ± 10 mm ² / s. Lubricant composition according to at least one of claims 1 to 3,
characterized in that
the sulfonate-based corrosion inhibitor is selected from the group comprising overbased and neutral Ca sulfonates, overbased and neutral Na sulfonates, and mixtures thereof, wherein
the composition
0.5 to 5 wt .-% overbased Na sulfonate, and / or
From 2 to 10% by weight of overbased Ca sulfonate,
and optionally in addition
1 to 5 wt .-% neutral Ca sulfonate, and / or
From 1 to 5% by weight of neutral Na sulfonate,
provided that the sum of the weight fractions of the sulfonate-based corrosion inhibitors is from 3 to 15% by weight of the total weight of the composition. A lubricant composition according to at least one of claims 1 to 4,
characterized in that
the composition - 1 to 5 wt .-% overbased Na sulfonate and 3 to 5 wt .-% overbased Ca sulfonate, more preferably 1.5 wt .-% overbased Na sulfonate and 3.5 wt .-% overbased Ca sulfonate , or - 1 to 5 wt .-% overbased Na sulfonate and 3 to 5 wt .-% overbased Ca sulfonate and 1 to 5 wt .-% neutral Ca sulfonate, more preferably 1.5 wt .-% overbased Na sulfonate and 3.5% by weight of overbased Ca sulfonate and 3% by weight of neutral Ca sulfonate, or - 3 to 6 wt .-% overbased Na sulfonate, particularly preferably 4.6 wt .-% overbased Na sulfonate, or From 3 to 10% by weight of overbased Ca sulphonate, more preferably 5.2% by weight of overbased Ca sulphonate, based on the total weight of the composition. A lubricant composition according to at least one of claims 1 to 5,
characterized in that
the composition in addition
0.05 to 1.7 wt .-% of at least one further inhibitor component based on the total weight of the composition,
wherein the further inhibitor component in the composition is preferably selected from
0.05 to 0.2 wt .-% triazoles, preferably 0.1 wt .-% benzotriazole or a benzotriazole derivatives, and / or
0.1 to 1.5% by weight of amines, preferably trialkanolamines. A lubricant composition according to at least one of claims 1 to 6,
characterized in that
the composition as ester component
10 to 20 wt .-% fatty acid ester or 1 to 5 wt .-% wool fat ester based on the total weight of the composition,
wherein the composition preferably comprises 15% by weight of fatty acid ester based on the total weight of the composition. Lubricating composition according to at least one of claims 1 to 7,
characterized in that
the composition
2 wt .-% phosphorus carrier component based on the total weight of the composition as a high pressure / anti-wear additive, wherein the phosphorus carrier component is particularly preferably dialkyl hydrogen phosphite, each alkyl having 14 to 22 carbon atoms. Lubricating composition according to at least one of claims 1 to 9,
characterized in that
the emulsifier is selected from nonionic surfactants, in particular fatty alcohol alkoxylates, which are preferably based on fatty alcohols having 16 to 18 carbon atoms and have a degree of ethoxylation of 2 to 5 mol, and mixtures thereof, and anionic surfactants, in particular alkyl ether carboxylic acids, more preferably a C _14-22 fatty alcohol polyglycol ether carboxylic acids, or phosphorus esters, especially alkoxylated fatty alcohol phosphate esters, more preferably phosphate esters of fatty alcohols having 16 to 18 carbon atoms and a degree of ethoxylation of 5 moles, and wherein a proportion of each component alone or in the mixture is in each case 1 to 5% by weight, based on the total weight of the composition, with the proviso that the total content of emulsifier does not exceed 15% by weight, the composition being preferred
7.5 wt .-% fatty alcohol alkoxylates as emulsifier based on the total weight of the composition, in particular 5 wt .-% C _16-18 - fatty alcohol having a degree of ethoxylation of 5 moles and 2.5 wt .-% C _16-18 - fatty alcohol with a degree of ethoxylation of 2 mol. Lubricating composition according to at least one of claims 1 to 9,
characterized in that
the carboxylic acid component is selected from carboxylic acids containing 16 to 22 carbon atoms, in particular tall oil fatty acid, oleic acid and behenic acid, or dimer acids which are dicarboxylic acids prepared by dimerization of tall oil unsaturated fatty acids, or mixtures thereof;
wherein the composition preferably comprises 0.5% by weight tall oil fatty acid based on the total weight of the composition. A lubricant composition according to at least one of claims 1 to 10,
characterized in that
the aminic antioxidant is a reaction product of N-phenyl-benzolamine with 2,4,4-trimethylpentene and
the phenolic antioxidant is selected from octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate and / or octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, wherein
the composition 0.25% by weight of aminic antioxidant and 0.25% by weight phenolic antioxidant, preferably octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, based on the total weight of the composition. Lubricating composition according to at least one of claims 1 to 11,
characterized in that
the wax and / or thickener component is selected from - paraffinic waxes, Castor oil derivatives, in particular thixotropic thickeners based on hydrogenated castor oil, Fatty acid derivatives, in particular fatty acid esters or fatty acid amides of C16-20 saturated and unsaturated fatty acids, - polymeric thickeners, wherein the composition preferably comprises 3 wt .-% paraffin wax with freezing point at 64 to 66 ° C as wax and / or thickener component. Cold washable dry lubricant composition for application on a metal strip as anticorrosive lubricant or prelube,
characterized in that
the composition
10 to 90% by weight wax component,
3 to 15% by weight of sulphonate-based corrosion inhibitor,
0.05 to 1.7% by weight of at least one further inhibitor component,
0.5 to 3 wt% phosphorus carrier component or 1 to 10 wt% sulfur carrier component as high pressure / antiwear additive,
0 to 15% by weight emulsifier,
0.05 to 1% by weight of carboxylic acid component,
0.05 to 1% by weight of aminic and / or phenolic antioxidant,
each based on the total weight of the composition. Use of a lubricant composition according to at least one of claims 1 to 12 or 13 for application to a metal strip as a corrosion protection, washing and / or forming lubricant, wherein the composition is cold washable with an alkaline-aqueous cleaner. Use according to claim 14,
wherein the surfactant concentration of the alkaline aqueous cleaner is adjusted to the emulsifier content of the lubricant composition.