EP2487227A1 - Reforming lubricant compound, in particular for cold forming of metallic parts - Google Patents

Abstract

Reforming lubricant composition (I) comprises 15-30 wt.% of at least one extreme-pressure additive, 8-55 wt.% of at least one unsaturated fatty acid or fatty acid ester, 7-20 wt.% of at least amine containing buffer agent, 2-12 wt.% of at least one wetting agent, and 5-15 wt.% of phosphoric acid and/or its derivative comprising organic and/or inorganic phosphate. Independent claims are included for: (1) the preparation of (I) comprising mixing the extreme pressure-additive, buffering agent and wetting agent, and further adding the phosphoric acid and/or its derivative comprising inorganic and/or organic derivatives, and the fatty acid or fatty acid ester or its derivatives; (2) coating to be formed metallic parts with (I) comprising applying (I); and (3) forming metallic parts, comprising applying (I) to be formed part and subsequently forming.

Description

The present invention relates to a forming lubricating composition, in particular for the cold forming of metallic parts, as well as a process for their preparation, a process for coating to be formed, in particular metallic, parts, as well as a process for the production of formed parts, in particular metallic parts.

By forming in particular metals, but also thermoplastics, plastically brought into a different form. A distinction is made between cold and hot forming. During cold forming, the deformation takes place below the recrystallization temperature of the material used, in the hot forming, however, there is regularly recrystallization of the material, which counteracts a solidification of the same. There are various types of forming such as pressure forming, tension forming, tensile forming, bending, shear forming and possibly also other forming processes. The forming takes place, for example, by rolling, free-forming, including swaging and driving, impressions, compression, deep-drawing, bending, and the like.

In order to reduce the friction as well as the forces to be used during forming, a wide variety of types of lubricants are used. In the cold forming, in particular, two types of lubricants are used, namely on the one hand, those which are liquid, and others, as such, which form a solid film on the parts to be formed. The disadvantage of the liquid lubricant is especially in the problem of processing, be it by film formation on floors, for example, whereby the risk of accidents is increased, be it by other contaminants of the immediate environment of the forming. In addition, there are basically problems with regard to the uniformity of the transformations, since the coating carried out by liquid lubricants is in motion during the forming process. Especially complicated transformations are often only feasible in view of the forming devices and forming tools used by lowering the forming forces, which, however, stabilize critical forming processes, since immediately the forming temperature decreases. There is therefore a need for forming lubricants, the scope of which is significantly expanded, including a reduction in the time between application and forming, and in particular surface pressures at higher pressures enable even with complicated transformations and with which lower coefficients of friction can be achieved.

These problems of liquid lubricants are not exhibited by those which form a solid film on the parts to be formed. However, as a rule, the corresponding lubricants have previously been dissolved in a solvent, for example water, the parts to be formed are subsequently treated with the solution and subsequently dried, which prolongs the processing time. The disadvantage of such solid lubricants, which are dissolved in particular in water, is in particular that their application is limited, which is due in particular to insufficient fluidity of the lubricant film formed on the part to be formed in the forming process, resulting in errors in the transformation or even damage the to be used tools of the forming device. In addition, with aqueous lubricants in the forming, in particular cold forming, in principle the problem that the most uniform film of the lubricant on the part to be formed must be produced, but this must not have too large thickness at the same time.

It is therefore an object of the present invention to provide a Umformschmiermittelzusammensetzung, in particular for the cold working of metallic parts, which eliminates the known from the prior art disadvantages, and in particular extends the scope of forming lubricants, and also achieved reduced coefficients of friction than also to provide a manufacturing method with a coating method based on this composition and a forming method using such a composition.

• mindestens ein EP-Additiv in einer Menge in einem Bereich von etwa 15 Gew.-% bis etwa 30 Gew.-%;
• mindestens eine/n mindestens einfach ungesättigte/n Fettsäure oder Fettsäureester in einer Menge in einem Bereich von etwa 8 Gew.-% bis etwa 55 Gew.-%;
• mindestens ein aminhaltiges Pufferungsmittel in einer Menge in einem Bereich von etwa 7 Gew.-% bis etwa 20 Gew.-%;
• mindestens ein Benetzungsmittel in einer Menge in einem Bereich von etwa 2 Gew.-% bis etwa 12 Gew.-%; und
• Phosphorsäure und/oder mindestens eines derer Derivate, umfassend organische und/oder anorganische Phosphate, in einer Menge in einem Bereich von etwa 5 Gew.-% bis etwa 15 Gew.-%;

wobei die Gew.-%-Bereiche jeweils bezogen sind auf die Gesamtmenge der Umformschmiermittelzusammensetzung.This object is achieved according to the invention by a forming lubricant composition, in particular for the cold forming of metallic components

• at least one EP additive in an amount ranging from about 15% to about 30% by weight;
• at least one at least monounsaturated fatty acid or fatty acid ester in an amount ranging from about 8% to about 55% by weight;
• at least one amine-containing buffering agent in an amount ranging from about 7% to about 20% by weight;
• at least one wetting agent in an amount ranging from about 2% to about 12% by weight; and
• Phosphoric acid and / or at least one of its derivatives comprising organic and / or inorganic phosphates in an amount ranging from about 5% to about 15% by weight;

wherein the wt .-% ranges are each based on the total amount of Umformschmiermittelzusammensetzung.

The reshaping lubricant composition according to the invention has the great advantage that, as tests have shown by means of cup-backward extrusion (NRFP), these lead to a reduction of the stamping force to be applied during forming by up to 30 kN in comparison to conventional lubricants, with error-free, In particular scarf-free formed parts can be obtained. As a result, the scope of the forming lubricant composition according to the invention is extended compared to those known from the prior art. In addition, the achievable friction coefficients are reduced by about 10%. Also, no so-called conversion layer is formed after application of this composition, so that an immediate transformation can take place.

The EP (Extreme Pressure) additive included in the composition of the invention is preferably contained therein in an amount ranging from about 20% to about 28% by weight. The EP additive is preferably selected from a group comprising derivatives of phosphoric acid, in particular phosphoric acid esters, more preferably alkylated or ethoxylated phosphoric acid esters. The preferred phosphoric acid esters can be selected from a group comprising primary, secondary and / or tertiary esters of orthophosphoric acid, and are preferably secondary or tertiary phosphoric acid esters. The phosphoric acid esters are preferably prepared in a reaction of phosphoric acid with straight-chain or branched alkyl alcohols having 1 to 12 carbon atoms and / or fatty alcohols having 12 to 24 carbon atoms. Particular preference is given to those phosphoric acid esters prepared in this way which have been subjected to ethoxylation, that is, in which at least one, preferably at least two -CH ₂ -CH ₂ -O groups have been inserted into the alkyl radical or fatty alcohol radical. Examples of suitable phosphoric acid esters as For the purposes of the present invention, EP additives are di-2-ethylhexyl phosphoric esters and ethoxylated fatty alcohol phosphoric esters.

The fatty acids or fatty acid esters used in the forming lubricant composition according to the invention can fulfill various functions. They can act as Reibwertverminderer, as control oil, or in specific embodiments as a further EP additive in addition to another EP additive, in particular as described above, act. Preferably, the at least one fatty acid or fatty acid ester or derivatives thereof is used in the composition of the present invention in an amount ranging from about 8% to about 59% by weight, more preferably to about 55% by weight. even more preferably in a range from about 20% to about 51% by weight, based on the total amount of the composition.

If the at least one fatty acid or the at least one fatty acid ester or derivatives thereof is to be used as a coefficient of friction reduction, these are preferably present in the composition according to the invention in an amount in a range of about 5% by weight, preferably about 8% by weight. to about 15% by weight, preferably to about 10% by weight, based on the total amount of the composition. Fric- tion-reducing fatty acids and / or fatty acid esters or their derivatives are preferably selected from a group comprising at least monounsaturated (free) fatty acids or fatty acid esters, also alkylated, in particular methylated, or ethoxylated, having at least monounsaturated fatty acid residues, and are preferably free fatty acids which are at least simple are unsaturated. The (free) fatty acids or fatty acid esters have in their fatty acid radical preferably 12 to 22, more preferably up to 20 carbon atoms, preferably 16 to 20 carbon atoms.

Particular preference is given to linoleic acid or linseed oil and oleic acid, in particular in the form of crude oleic acid, tallow fatty acids, tall oil and / or tall oil fatty acid, where olein can also comprise palmitic and stearic acid in addition to oleic acid, as well as glycerol mono- and dioleates in addition to trioleates , or derivatives of said substances, in particular alkylated, in particular methylated, or ethoxylated. Also, mixtures of the substances mentioned are possible.

Instead of linseed oil or derivatives of linseed oil, ie, for example, methylated or ethoxylated linseed oil, linoleic acid or linolenic acid, alone and in admixture, can also be used. optionally also with the addition of oleic acid and / or tall oil or tall oil fatty acid, as fatty acid or in the form of derivatives thereof, in particular in the form of alkyl fatty acid esters.

Particularly preferably, the fatty acid and / or the fatty acid ester is selected as Reibwertverminderer selected from a group comprising fatty acids or fatty acid esters having 16 to 24 carbon atoms. More preferably, the fatty acid and / or fatty acid esters are at least monounsaturated, more preferably selected from a group comprising oleic acid, linoleic acid and / or linolenic acid and / or tall oil fatty acid, individually or in admixture, or their corresponding fatty acid esters when using fatty acid esters. Particularly preferably, at least some of the fatty acids and / or fatty acid esters used have conjugated double bonds.

If the at least one fatty acid and / or the at least one fatty acid ester or its derivatives are used as control oil, preferably in addition to or in combination with other control oils, these are preferably selected from a group comprising at least monounsaturated fatty acids and / or fatty acid esters comprising monounsaturated fatty acid esters, in particular ethoxylated, more preferably those having an alkyl radical having 1 to 6 carbon atoms. Particularly preferred are alkyloleates, more preferably methyloleate. If fatty acids and / or fatty acid esters are used as (single) control oils in the composition according to the invention, they are preferably present in the composition in an amount ranging from about 3% by weight to about 45% by weight, preferably to about 30% by weight %, based on the total amount of the composition. If another control oil, not based on fatty acids and / or fatty acid esters, is included in the composition according to the invention, the fatty acid and / or fatty acid esters or their derivatives are advantageously present in an amount ranging from about 3% by weight to about 15% by weight. %, preferably up to 8% by weight, based on the total amount of the composition, of this.

The at least monounsaturated fatty acid and / or fatty acid esters as control oil, as defined above, may also be sulfurized, but are preferably unsulfurized. Preferably, these have 12 to 22 carbon atoms in the fatty acid or the fatty acid radical. The proportion of at least monounsaturated fatty acid or fatty acid ester is at least about 80 wt .-%, preferably at least about 90% by weight, up to about 99% by weight, preferably up to about 95% by weight, based on the total fatty acid or total fatty acid ester.

If the at least one fatty acid and / or fatty acid ester or derivatives thereof fulfill the function of a (further) EP additive, then these are advantageously selected from a group comprising at least monounsaturated fatty acids and / or fatty acid esters, more preferably at least partially sulfurized, more advantageously at least partially sulfurized, having a sulfur content in a range from about 5% to about 30%, preferably from about 8% to about 20% by weight, based on the total amount of fatty acid and / or fatty acid ester , Sulfurated fatty acid esters, which can be used as an EP additive, preferably have straight-chain or branched alkyl radicals having 1 to 12 carbon atoms. If fatty acids and / or fatty acid esters are used as further EP additives in the composition according to the invention, they are present in the composition according to the invention in an amount ranging from about 7% by weight to about 30% by weight, more preferably in one range from about 7.5% to about 26% by weight, based on the total amount of the composition.

Further advantageously, the composition according to the invention comprises at least one free, at least monounsaturated fatty acid and / or at least one at least monounsaturated fatty acid ester, preferably both at least one free, at least monounsaturated fatty acid and at least one at least monounsaturated fatty acid ester. With regard to the chemical structure and the weight% ranges to be used, reference is made to the above statements. If at least one fatty acid or the at least one fatty acid ester is used in a composition as an adjusting oil and also as an EP additive, these may optionally be chemically identical, depending on the further constituents of the composition. If a fatty acid ester is used as the control oil, it is preferably non-sulfurized and further preferably has a kinematic viscosity in a range from about 5 to about 15 cSt (corresponding to about 5 to about 15 mm ² / s ^-1 ), measured according to DIN 51562 at 40 ° C, on, when used as an EP additive, it is preferably used sulfurized, preferably with a kinematic viscosity in a range of about 16 to about 250 cSt (corresponding to about 16 to about 250 mm ² / s ^-1 ), preferably from about 18 to about 150 cSt (corresponding to about 18 to about 150 mm ² / s ^-1 ), measured according to DIN 51562 at 40 ° C.

The amine-containing buffering agent according to the composition of the invention is advantageously in a range from about 8% to about 15% by weight, more preferably in a range from about 9% to about 14% by weight, in the present invention Composition present, based in each case on the total amount of the composition. The amine-containing buffering agent is advantageously selected from a group comprising fatty amines, in particular fatty amines having a fatty acid radical having at least one unsaturated carbon-carbon double bond. Further advantageously, the amine-containing buffering agent is selected from a group comprising ethoxylated fatty amines, wherein at least one, preferably at least two -CH ₂ -CH ₂ -O-groups are included in the fatty amine. Particularly preferred buffering agents in the context of the present invention are soya oil and rapeseed fatty amines obtained from rapeseed oil and soybean oil, as well as oleic amines (oleylamines), particularly preferably ethoxylated fatty amines of the substances mentioned. Particularly preferred are tertiary ethoxylated fatty amines, but also primary and secondary fatty amines, in particular ethoxylated, are excluded in the context of the present invention as a buffering agent.

The wetting agent further included in the composition of the present invention is advantageously present therein in an amount ranging from about 3% to about 10% by weight, more preferably ranging from about 4% to about 9% by weight .-%, based on the total amount of the composition. The wetting agent is advantageously selected from a group comprising sulfonic acids and their derivatives, in particular derivatives of alkylbenzenesulfonic acids, in particular of dodecylbenzenesulfonic acid, in particular in the form of salts, but also in free form. Particularly preferred is the use of amine salts of sulfonic acids, especially alkylbenzenesulfonic acids, more preferably the use of triethanolamine dodecylbenzylsulfonate.

The phosphoric acid and / or at least one of its derivatives comprising inorganic and / or organic phosphates is preferably present in an amount ranging from about 6% to about 12% by weight, based on the total amount of the composition contain. In the context of the present invention to be used derivatives of phosphoric acid are preferably amine phosphates, more preferably primary amine phosphates, even more preferably primary amine phosphates having a tertiary amine radical, preferably straight-chain alkyl radicals having 1 to 12, or 2 to 6, carbon atoms, preferably methyl, ethyl -, Propylreste has. Especially preferred For the purposes of the present invention is primary triethanolamine phosphate. Advantageously, the amine phosphate is prepared immediately prior to preparation of the composition of the invention from a tertiary amine, for example triethanolamine, and aqueous phosphoric acid. Inorganic phosphoric acid derivatives that can be used in the composition of the present invention include, for example, primary sodium phosphate, primary calcium phosphate, or primary strontium phosphate, which are preferably prepared in situ from phosphoric acid and the corresponding alkali or alkaline earth carbonate.

Insofar as the term "about" is used in the claims and the description of the present application, it is readily apparent to the person skilled in the art that the stated range limits are not rigid limits, but rather also slight deviations from this, the object and purpose and the present invention Fulfill invention. In particular, deviations of +/- 5%, more preferably +/- 2%, from the stated range limits are those which fall within the scope of the present invention.

The composition according to the invention also advantageously comprises at least one control oil, preferably not based on, in particular, at least monounsaturated fatty acids and / or fatty acid esters, in an amount of from about 12% by weight to about 30% by weight, more preferably in an amount from about 16% to about 25% by weight, based on the total amount of the composition. Advantageously, the control oil is selected from a group comprising at least one polyalkylene glycol or a derivative thereof.

Advantageously, the polyalkylene glycol is selected from a group comprising at least one polyethylene glycol and / or polypropylene glycol or derivatives thereof, with particular preference being given to derivatives of polyethylene glycol having an average molecular weight in a range from about 10,000 to about 40,000, more preferably from about 21,000 to about 38,000 more preferably about 24,000 to about 36,000. Particularly preferred are polyethylene glycol fatty acid ester derivatives, more preferably those which have at least one unsaturated double bond in the fatty acid radical, more preferably polyethylene glycol monooleate. Polyethylene glycol fatty acid derivatives, especially monooleates, are preferably employed having a molecular weight in a range of from about 100 to about 2000, more preferably from about 200 to 1000, even more preferably in a range from about 300 to about 700.

The polyalkylene glycol derivatives used have the general formula R ³ O - [- R ¹ -OR ² -O] _n -H, but can also be used as block polymers having the general formula R ³ O - (- R ¹ -O-) _x - (- R ² -O) _x -H be formed. Examples of these are derivatives of polyethylene glycol with R ¹ = R ² = (CH ₂ ) ₂ , polypropylene glycol with R ¹ = R ² = CH ₂ -CH (CH ₃ ) or polytetramethylene glycol with R ¹ = R ² = (CH ₂ ) ₄ , and the mentioned block polymers may in particular be mixtures of the abovementioned radicals R ¹ and R ² . In the derivatives, the radical R ^{3 may be} an alkyl radical having 1 to 24 carbon atoms, but may also be a fatty acid ester having 12 to 22 carbon atoms, also partially unsaturated, preferably having at least one carbon-carbon double bond.

The composition according to the invention particularly preferably has an actuating oil based on at least one polyalkylene glycol derivative, as described above, and an (at least) monounsaturated (free) fatty acid or fatty acid ester acting as an adjusting oil. In this case, the at least one fatty acid and / or fatty acid ester is contained in an amount of preferably 4 wt .-% to about 8 wt .-% in the mixture according to the invention, and the control oil based on a polyalkylene glycol in an amount of about 15 wt. -% to about 25 wt .-%, each based on the total amount of the composition. Preferably in this embodiment at least one fatty acid ester, preferably an at least monounsaturated fatty acid ester, is used, more preferably an alkyl oleate, even more preferably methyl oleate. In this embodiment, the polyalkylene glycol is advantageously selected from a group comprising polyethylene glycol or derivatives thereof, preferably polyethylene glycols esterified with fatty acids, even more preferably polyethylene glycol monooleate.

As an actuating oil, it is also possible to use esters of carboxylic acids having 2 to 6 carbon atoms, particular preference being given to ethyl esters and propane esters. These alkyl esters are particularly preferably esterified with tertiary alkylol radicals, for example trimethylol or triethylol radicals. Particular preference is given to using a trimethylolpropane ester. With regard to the weight% ranges, what has been said above for other control oils, in particular based on at least monounsaturated fatty acids and / or fatty acid esters, applies.

The composition of the invention further advantageously further comprises a reaction accelerator in an amount of from 0.05% to about 2.5% by weight preferably in an amount of about 0.1% to about 2% by weight, more preferably in an amount of about 0.15% to about 0.5% by weight, based in each case on Total amount of the composition. The reaction accelerator is advantageously selected from a group comprising benzoic acid or its derivatives, and is preferably 3,5 dinitrobenzoic acid. However, derivatives such as salts of benzoic acid, for example triethanolamine salts of 3,5-dinitrobenzoic acid, can also be used, or else salts of nitroacids, in particular of nitrosulfonic acids.

• mindestens ein EP-Additiv auf Basis eines Phosphorsäureesters in einer Menge in einem Bereich von etwa 20 Gew.-% bis etwa 28 Gew.-%;
• mindestens eine/n zumindest teilweise geschwefelte/n, insbesondere mindestens einfach ungesättigte/n, Fettsäure oder Fettsäureester, nämlich als weiteres EP-Additiv, in einer Menge in einem Bereich von etwa 7,5 Gew.-%, bevorzugt von etwa 20 Gew.-%, bis etwa 40 Gew.-%;
• mindestens ein ethoxyliertes Fettsäureamin als Pufferungsmittel in einer Menge in einem Bereich von etwa 7 Gew.-% bis etwa 15 Gew.-%;
• mindestens ein Salz einer Sulfonsäure als Benetzungsmittel in einer Menge in einem Bereich von etwa 3 Gew.-% bis etwa 11 Gew.-%;
• mindestens ein primäres Aminphosphat in einer Menge in einem Bereich von etwa 6 Gew.-% bis etwa 10 Gew.-%;
• mindestens einen mindestens einfach ungesättigten Fettsäureester oder einen Alkylester, nämlich als Stellöl, in einer Menge in einem Bereich von etwa 20 Gew.-% bis etwa 40 Gew.-%;

wobei die Gewichtsprozente bezogen sind auf die Gesamtmenge der Zusammensetzung.Particularly preferred is a composition of the invention comprising

• at least one EP additive based on a phosphoric acid ester in an amount ranging from about 20% to about 28% by weight;
• at least one at least partially sulfurized, in particular at least monounsaturated, fatty acid or fatty acid ester, namely as further EP additive, in an amount in the range of about 7.5% by weight, preferably about 20% by weight. -%, to about 40 wt .-%;
• at least one ethoxylated fatty acid amine buffering agent in an amount ranging from about 7% to about 15% by weight;
• at least one salt of a sulfonic acid wetting agent in an amount ranging from about 3% to about 11% by weight;
• at least one primary amine phosphate in an amount ranging from about 6% to about 10% by weight;
• at least one at least monounsaturated fatty acid ester or an alkyl ester, namely as a control oil, in an amount ranging from about 20% to about 40% by weight;

wherein the weight percentages are based on the total amount of the composition.

In the composition defined above, the at least one fatty acid and / or at least one fatty acid ester or derivatives thereof is once in its function as an EP additive in the form of the at least partially sulfurized fatty acid or fatty acid ester, especially at least monounsaturated, used, and once as a control oil as at least monounsaturated fatty acid esters.

• mindestens ein EP-Additiv auf Basis eines Phosphorsäureesters, vorzugsweise ethoxyliert, in einer Menge in einem Bereich von etwa 20 Gew.-% bis etwa 28 Gew.-%;
• mindestens eine/n zumindest teilweise geschwefelte/n, vorzugsweise mit einem Schwefelgehalt in einem Bereich von etwa 5 Gew.-% bis etwa 30 Gew.-%, bezogen auf die Gesamtmenge der Fettsäure bzw. des Fettsäureesters, insbesondere zumindest einfach ungesättigte/n, Fettsäure oder Fettsäureester, nämlich als weiteres EP-Additiv, in einer Menge in einem Bereich von etwa 8 Gew.-% bis etwa 15 Gew.-%;
• mindestens ein ethoxyliertes Fettsäureamin als Pufferungsmittel in einer Menge in einem Bereich von etwa 7 Gew.-% bis etwa 15 Gew.-%;
• mindestens ein Salz einer Sulfonsäure als Benetzungsmittel in einer Menge in einem Bereich von etwa 6 Gew.-% bis etwa 10 Gew.-%;
• mindestens ein primäres Aminphosphat in einer Menge in einem Bereich von etwa 6 Gew.-% bis etwa 10 Gew.-%;
• als Stellöl mindestens ein Polyethylenglykol in einer Menge in einem Bereich von etwa 15 Gew.-% bis etwa 25 Gew.-% mit einem mittleren Molekulargewicht in einem Bereich von etwa 100 bis etwa 2000, bevorzugt von etwa 200 bis etwa 1000, weiter von bevorzugt etwa 300 bis etwa 700;
• mindestens einen mindestens einfach ungesättigten, bevorzugt ungeschwefelten Fettsäureester in einer Menge in einem Bereich von etwa 3 Gew.-% bis etwa 8 Gew.-%, nämlich als weiteres Stellöl;
• mindestens eine mindestens einfach ungesättigte Fettsäure mit 16 bis 22 Kohlenstoffatomen in einer Menge in einem Bereich von etwa 8 Gew.-% bis etwa 15 Gew.-%, nämlich als Reibwertverminderer; sowie
• mindestens einen Reaktionsbeschleuniger in einer Menge von etwa 0,1 Gew.-% bis etwa 0,3 Gew.-%;

wobei die Gewichtsprozente bezogen sind auf die Gesamtmenge der Zusammensetzung.A further, particularly preferred composition according to the invention comprises

• at least one EP additive based on a phosphoric acid ester, preferably ethoxylated, in an amount ranging from about 20% to about 28% by weight;
• at least one at least partially sulfurized oil, preferably having a sulfur content in a range from about 5% by weight to about 30% by weight, based on the total amount of the fatty acid or fatty acid ester, in particular at least monounsaturated / n, Fatty acid or fatty acid ester, namely, as another EP additive, in an amount ranging from about 8% to about 15% by weight;
• at least one ethoxylated fatty acid amine buffering agent in an amount ranging from about 7% to about 15% by weight;
• at least one salt of a sulfonic acid wetting agent in an amount ranging from about 6% to about 10% by weight;
• at least one primary amine phosphate in an amount ranging from about 6% to about 10% by weight;
• as the control oil at least one polyethylene glycol in an amount ranging from about 15 wt .-% to about 25 wt .-% having an average molecular weight in a range of about 100 to about 2000, preferably from about 200 to about 1000, more preferably about 300 to about 700;
• at least one at least monounsaturated, preferably non-sulfurized, fatty acid ester in an amount ranging from about 3% to about 8% by weight, namely, as another control oil;
• at least one at least monounsaturated fatty acid having from 16 to 22 carbon atoms in an amount ranging from about 8% to about 15% by weight, namely, as a coefficient of friction reducer; such as
• at least one reaction accelerator in an amount of about 0.1% to about 0.3% by weight;

wherein the weight percentages are based on the total amount of the composition.

In this further preferred composition, in turn, the at least one fatty acid and / or at least one fatty acid ester is used as EP additive in the form of an at least partially sulfurized fatty acid or fatty acid ester, preferably fatty acid ester, in particular at least monounsaturated, as well as in its function as actuating oil, preferably an alkyl oleate, but in substantially smaller amounts than in the composition of the invention as defined above. Instead, the main task of the control oil now assumes at least one polyethylene glycol, advantageously a polyethylene glycol fatty acid derivative, even more preferably a polyethylene glycol monooleate. The polyethylene glycol preferably has an average molecular weight in a range of about 300 to about 950. Furthermore, the at least one fatty acid and / or at least one fatty acid ester in its function as Reibwertverminderer in the form of an at least monounsaturated free fatty acid, advantageously a linseed oil fatty acid, comprises of this specific composition according to the invention.

The present invention furthermore relates to a process for preparing a composition according to the invention as described above, which comprises initially introducing a mixture of EP additive, buffering agent and wetting agent into this mixture phosphoric acid or at least one of its derivatives selected from inorganic or organic phosphates, is added, and then the at least one fatty acid and / or fatty acid esters are added. Further advantageously, a reaction accelerator is added before admixing phosphoric acid and / or at least one of their derivatives. More preferably, in the inventive method after admixture of the phosphoric acid or at least one of these derivatives at least one control oil added. The control oil is selected from a group comprising at least one polyalkylene glycol or at least one fatty acid and / or fatty acid esters, as described above. If an organic derivative of phosphoric acid is used, it is separated immediately before it is added prepared by reaction of a suitable alcohol or amine, preferably a tertiary amine, with phosphoric acid. Sulfurized fatty acids or fatty acid esters are used as EP additives in particular, these are presented together with the wetting agent, the buffering agent and the actual EP additive, which is not based on fatty acids and / or fatty acid esters. If a fatty acid and / or fatty acid ester is added as a friction-reducing agent, it is preferably added after addition of phosphoric acid and / or at least one of its derivatives. If, in addition to at least one polyalkylene glycol, another control oil in the form of at least one fatty acid and / or fatty acid ester or in the form of an alkyl ester is present, it is preferably added last to the mixture and the desired viscosity of the mixture according to the invention is set therewith.

Furthermore, the present invention relates to a method for coating, in particular metallic, parts, with the composition according to the invention, wherein by a suitable method, for example by dipping, spraying or application by means of a application tool, for example a roll or a cloth, the composition is applied to the parts to be formed. After application, superfluous lubricant is drained off, and the part coated in such a way that it is to be formed is stored, for example in the bunker of a forming device.

Finally, the present invention relates to a method for forming metallic parts using the composition according to the invention, wherein the composition according to the invention is applied to the parts to be formed prior to forming and this part to be reshaped is subsequently formed. After reshaping any residues from the formed part removed, which can be done especially by hand wiping. Advantageously, it has been found that the forces to be applied in forming by use of the composition according to the invention are reduced in comparison with the use of such compositions known from the prior art, as well as the measured coefficients of friction.

These and other advantages of the present invention will become apparent from the following examples. It should be pointed out at this point that the examples are not intended to limit the scope of the present invention, but are merely illustrative. In particular, the features specified in the description, including the examples, can be combined with each other for further training.

The following substances or additives were used in the example forming lubricant compositions:

Polyalkylene glycol derivative

Here, a polyethylene glycol monooleate (hereinafter "PEG-MO" called) having an average molecular weight of about 400 was used, available under the name Ligalube PEG 400 MO, obtained from the company Peter Greven GmbH & Co. KG, Bad Münstereifel, Germany , used as control oil.

EP additive

The EP additive used was a di-2-ethylhexyl phosphoric acid ester, available under the product name Hordaphos MDAH, Clariant GmbH, Frankfurt / Main, Germany, hereinafter referred to as Hordaphos, or an ethoxylated fatty alcohol phosphoric acid ester, available under the name Lubrophos LB 400 E, from the company Rhodia, purchased from the company CH Erbslöh KG, Krefeld, Germany, hereinafter referred to as "Lubrophos" used.

Fatty acid or fatty acid ester

Linseed oil fatty acid, obtained from the company Carroux Handelsgesellschaft mbH, Geesthacht, Germany, was used as a friction value reducer, hereinafter referred to as "LÖFS". The control oil used was methyl oleate, obtained from the company FB Silbermann GmbH & Co., Gablingen, Germany, hereinafter referred to as "MO". The EP additive used was sulfurized olein, available under the name "Becrosan GO 10" from Lubrizol France, Rouen, France, containing about 9% by weight of sulfur (hereafter "becrosan"), or a sulfurized fatty acid methyl ester. available under the name "Additin RC 2818" from RheinChemie Rheinau GmbH, Mannheim, Germany, which contains about 18 wt .-%, based on the total amount of the fatty acid ethyl ester, sulfur and a proportion of at least monounsaturated fatty acid in the total fatty acid of about 90% by weight (hereinafter called "additin").

buffering

Buffering agent used was either an ethoxylated soybean safflower, available under the name "Berol 302" from Akzo Nobel Surface Chemistry AB, Stenungsund, Sweden, and obtained from Julius Hoesch GmbH & Co. KG, Dueren, Germany, hereinafter "Berol". called, an ethoxylated oleinamine, available under the name "Genamin O 20" from Clariant GmbH, Frankfurt / Main, Germany, hereinafter referred to as "Genamin", or an ethoxylated oleylamine, available under the name Ethomeen OV / 17 from the company Akzo Nobel Surface Chemistry AB, Stenungsund, Sweden, and used by the company Julius Hoesch GmbH & Co. KG, Düren, Germany, hereinafter referred to as "Ethomeen" used.

Wetting agent

The wetting agent used was a triethanolamine salt of dodecylbenzenesulfonic acid, available under the name "Marlopon AT 50", obtained from Brenntag AG, Mülheim / Ruhr, Germany, hereinafter referred to as "Marlopon", or a dodecylbenzenesulfonic acid designated lumoic acid A, available from Julius Hoesch GmbH & Co. KG, Düren, Germany, from Zschimmerer & Schwarz, hereinafter referred to as "luma acid".

phosphoric acid derivative

The phosphoric acid derivative used was primary triethanolamine phosphate (hereinafter referred to as TEAP), which was prepared immediately before preparation of the composition from five parts of triethanolamine, one part of water and four parts of 80% aqueous phosphoric acid by mixtures in a stainless steel container and cold stirring thereof, also primary alkali or alkaline earth metal phosphates prepared in situ from phosphoric acid and the corresponding alkali or alkaline earth metal derivative.

reaction accelerators

The reaction accelerator was either 3,5-dinitrobenzoic acid from Sigma-Aldrich Chemie GmbH, Steinheim, Germany, hereinafter referred to as "DNB", or a triethanolamine salt thereof, prepared by mixing triethanolamine and 3,5-dinitrobenzoic acid with stirring, for clarity, hereinafter referred to as "TEM DNB" used.

Alkyl ester as an actuating oil

Furthermore, the control oil used was a trimethylolpropane ester with the name "Priolube 3999" from Unichema, obtained from Croda GmbH, Nettetal, Germany, hereinafter referred to as "priolube".

Incidentally, as far as necessary, water was used in the form of distilled water or phosphoric acid. Exemplary compositions according to the invention are shown in Table 1 below. <b> Table 1 </ b> [Wt .-%] A B C D e F G H I Control oil based on fatty acid esters or alkyl esters 25 (MO) 25 (MO) 25 (MO) 25 (MO) 25 (MO) 24.0 (MO) 25.5 (Priolube) 35.5 (MO) 5.8 (MO) EP additive, not based on fatty acid and / or fatty acid esters 25 (Hordaphos) 25.0 (Hordahpos) 25.0 (Hordaphos) 25.0 (Hordophos) 25.0 (Hordophos) 25.0 (Hordophos) 25.0 (Hordophos) 25.0 (Hordophos) 25 (Lubropho s) buffering 10 (Ethomeen) 10.0 (Berol) 10.0 (Berol) 10.0 (Berol) 10.0 (Berol) 10.0 (Berol) 10.0 (Berol) 10.0 (Berol) 13 (Genamin) EP additive (sulphurised fatty acid or fatty acid ester) 25 (Becrosan) 25 (Becrosan) 25 (Becrosan) 25 (Becrosan) 25 (Becrosan) 25 (Becrosan) 25 (Becrosan) 15.0 (Additin) 10 (additin) Wetting agent 5 (luma acid) 4,5 (Marlopon) 4,5 (Marlopon) 4,5 (Marlopon) 4,5 (Marlopon) 4,5 (Marlopon) 4,5 (Marlopon) 4,5 (Marlopon) 8 (Marlopon) Phosphoric acid or phosphoric acid derivative 10 H ₃ PO ₄ (80%) 8 NaH ₂ PO ₄ 8 CaHPO ₄ 8 SrHPO ₄ 8 (TEAP) 8 (TEAP) 8 (TEAP) 8 (TEAP) 8 (TEAP) Control oil based on PEG-MO 20.0 reaction accelerators 1.5 TEM DNB 0.2 (DNB) linseed oil fatty acid 10 (LÖFS) water 2.0 2.0 2.0 2.0 2.0 2.0 2.0

The mixtures A to I listed above in Table 1 were prepared as described above, which were subsequently cross-cut into the mixture and before filling by means of a colloid mill and filled through a filter with a gap width of 30 microns.

As a comparative forming lubricant to the lubricants of the invention, the lubricant IRMCO Fluid 980 680, available on the company Ibi oil free division GmbH, Dirmstein, Germany, was used.

Firstly, with the mixture G and the comparative forming lubricant, cup-reverse extrusion tests were carried out on cylindrical blanks with a diameter of 19.95 mm and a height of 25 mm made of a case hardening steel C15 (with the German material standard 1.0401). As a forming machine such a May-Pressenbau GmbH was used with the type designation MKN2-600 / 14F. The specimens were immersed in the mixture G or the comparative forming lubricant, drained, and then placed in the press. Force-displacement diagrams were recorded and the specimens subsequently examined. In total, up to eight specimens were subjected to reshaping.

The force-displacement diagrams of specimens treated with mixture G showed that a stamping force of about 350 kN on average had to be used, whereas in the comparison-conversion lubricant forces of about 375 kN on average had to be used. In addition, the specimens treated with the comparative forming lubricant exhibited scoring after forming and were therefore not optically perfect.

In addition, mixtures H and I were used to produce monoblock shafts with stepped toothing from a cylindrical body of 25CrMo4 with a total length of 42.5 cm and a maximum diameter of 29.64 mm. In addition, after coating the specimens with the compositions H and I, they were additionally treated with a hammer oil with the name "Ilocut460" from BP Europe SE, Möchengladbach, Germany. Again, force-displacement diagrams, in this case the pulling force, were recorded, the forming force being almost constant at 180 kN for mixture H and at 175 kN for mixture I. In addition, a double-cup extrusion test (DCET) was carried out with mixtures G and F (see for DCET Geiger, R .: The material flow in combined cup extrusion in: Lange, K. (Editor): Reports from the Institute for Forming Technology of the University of Stuttgart, Report No. 36, Essen: Verlag W. Girardet, 1976 ). The specimens were made of case hardening steel 16MnCrS5 (with the German material number 1.7131) manufactured as cylindrical pipe parts with a diameter of 19.9 mm and a height of 24 mm. These were placed in a forming tool that was adaptable to the dimensions of said specimens, the upper and lower punches being identical and having punch diameters of 16 mm. The diameter of a controllable and temperature-controlled die in the forming tool was 20 mm. As a forming device, a forming machine of May-Pressenbau GmbH with the name MKN 2-600 / 14F, a double-column toggle press was used. The specimens were coated with the mixture H and I in a dip bath, then drained, and then placed in the forming tool. The DCET tests showed a reduction in the coefficient of friction in the mixture I over mixture H by more than 20%, on average, the applied force after recording force-displacement diagrams by about 5 kN to 7 kN in the mixture I compared to the mixture G are lowered. Also, the pond depth ratios in the mixture I were always less than 2, based on a total of seven examined samples, whereas in the case of the mixture H this was the case only for two samples.

By means of the composition according to the invention and the processes according to the invention, it is thus possible to advantageously shape, in particular, metallic parts by reducing the forces to be applied and the coefficients of friction, especially even in the case of complicated transformations, thereby considerably expanding the field of application of the compositions according to the invention in comparison with those of the prior art is.

Claims (13)

Forming lubricant composition, in particular for the cold forming of metallic parts, comprising at least one EP additive in an amount ranging from about 15% to about 30% by weight; at least one at least monounsaturated fatty acid or fatty acid ester in an amount ranging from about 8% to about 55% by weight; at least one amine-containing buffering agent in an amount ranging from about 7% to about 20% by weight; at least one wetting agent in an amount ranging from about 2% to about 12% by weight; and Phosphoric acid and / or at least one of its derivatives, comprising organic and / or inorganic phosphates, in an amount ranging from about 5% to about 15% by weight; wherein the wt .-% ranges are each based on the total amount of Umformschmiermittelzusammensetzung. The composition of claim 1, further comprising at least one control oil in an amount ranging from about 12% to about 30% by weight, based on the total amount of the composition. A composition according to claim 2, characterized in that the control oil is selected from a group comprising at least one polyathylene glycol or a derivative thereof. A composition according to any one of the preceding claims, further comprising at least one reaction accelerator in an amount of from about 0.05% to about 2.5% by weight, based on the total amount of the composition. Composition according to one of the preceding claims, comprising at least one free, at least monounsaturated fatty acid and / or at least one at least monounsaturated fatty acid ester. Composition according to any one of the preceding claims, characterized in that the fatty acid and / or the fatty acid ester is sulphurised with a sulfur content of from about 5% to about 30% by weight relative to the total of the fatty acid and / or of the fatty acid ester. A composition according to any one of the preceding claims comprising at least one EP additive based on a phosphoric acid ester in an amount ranging from about 20% to about 28% by weight; at least one at least partially sulphurised or especially at least monounsaturated fatty acid or fatty acid ester in an amount in a range from about 7.5% by weight, preferably from about 20% by weight to about 40% by weight. -%; at least one ethoxylated fatty amine as a buffering agent in an amount ranging from about 7% to about 15% by weight; at least one salt of a sulfonic acid wetting agent in an amount ranging from about 3% to about 11% by weight; at least one primary amine phosphate in an amount ranging from about 6% to about 10% by weight; at least one at least monounsaturated fatty acid ester or alkyl ester in an amount ranging from about 20% to about 40% by weight; wherein the weight percentages are each based on the total amount of the composition. A composition according to any one of claims 1 to 6 comprising at least one EP additive based on a phosphoric acid ester in an amount ranging from about 20% to about 28% by weight; at least one at least partially sulfurized, in particular at least monounsaturated fatty acid or fatty acid ester in an amount ranging from about 8% to about 15% by weight; at least one ethoxylated fatty amine as a buffering agent in an amount ranging from about 7% to about 15% by weight; at least one salt of a sulfonic acid as wetting agent in an amount ranging from about 6% to about 10% by weight; at least one polyethylene glycol in an amount in a range from about 15% by weight to about 25% by weight with an average molecular weight in a range from about 100 to about 2000; such as at least one primary amine phosphate in an amount ranging from about 6% to about 10% by weight; at least one at least monounsaturated fatty acid ester in an amount ranging from about 3% to about 8% by weight; at least one at least monounsaturated fatty acid having from 16 to 22 carbon atoms in an amount ranging from about 8% to about 15% by weight; at least one reaction accelerator in an amount of about 0.1% to about 0.3% by weight; wherein the weight percentages are each based on the total amount of the composition. A process for the preparation of compositions according to any one of claims 1 to 8, characterized in that a mixture of EP additive, buffering agent and wetting agent is initially added, phosphoric acid and / or at least one of these derivatives comprising inorganic and / or organic derivatives, admixed, and subsequently at least one fatty acid or fatty acid ester or derivatives thereof is added. A process according to claim 9, wherein a reaction accelerator is added before admixing the phosphoric acid and / or at least one of its derivatives. Method according to one of claims 9 or 10, characterized in that after admixture of phosphoric acid and / or at least one of these derivatives at least one control oil is added. Process for coating metallic, in particular metallic, parts to be shaped with a composition according to one of Claims 1 to 8, characterized in that the composition is applied to the parts to be formed by a suitable process. A process for producing shaped, in particular metallic, parts, characterized in that a composition according to one of claims 1 to 8 is applied to the part to be formed prior to forming and this is subsequently formed.