EP2828419B1 - Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate - Google Patents

Description

The corrosion protection system comprises carboxylic and / or phosphonic acids and at least one amine having at least one oxybis (alkylamine) unit. Such anticorrosive systems effectively protect metal surfaces from corrosion and have high water solubility, which is indispensable for the formulation of aqueous concentrates for metalworking and metalworking fluids. The present invention relates to an aqueous surface-active and corrosion-protective preparation comprising the corrosion protection system and an emulsifier system and an oily, water-miscible emulsion concentrate which, when diluted with water, provides ready-to-use corrosion protection, cleaning and cooling lubricant emulsions.

The protection of corrosion-prone metals such as iron, aluminum, zinc, copper or their alloys against corrosion is a widespread technical task. It arises in particular when the metal parts are not or not yet covered with a permanent corrosion-protective coating such as a paint due to their processing condition or because of their field of application. Examples include metal parts during technical processing stages such as machining or non-cutting shaping or cleaning and finished metal components such as heat exchangers or pipelines, which come into contact during their function with corrosive aqueous media. In order to prevent or limit corrosion during or between the individual processing steps or during normal use, the metal surfaces are brought into contact with corrosion inhibitors, which cause a temporary corrosion protection. It is often desirable for reasons of environmental protection that the corrosion inhibitors in the aqueous phase can be brought into contact with the metal surfaces. In addition, most metalworking or metalworking fluids are based on aqueous formulations so that the water solubility of a corrosion inhibitor for the formulation of these Preparations is essential. Therefore, it is a desirable property of corrosion inhibitors to be water soluble.

As water-soluble corrosion inhibitors, a variety of inorganic and organic compounds are known. Inorganic corrosion inhibitors may be based, for example, on chromates, nitrites or phosphates, but these are more or less disadvantageous for toxicological and ecological reasons. Organic corrosion inhibitors are often based on carboxylates, amines, amides or on nitrogen-containing heterocyclic compounds. Carboxylic acids as such, however, prove in practice to be insufficiently long-term effective if the pH is lowered by an acid entry into the inhibitor baths or by microbiological processes to such an extent that the carboxylic acids are present in the less active acid form instead of in the salt form. Corrosion-inhibiting carboxylic acids are therefore often used in the form of their salts or as a corrosion protection system consisting of the carboxylic acid and a base. Particularly well-known in the art are corrosion protection systems consisting of carboxylic acids and alkanolamines, which have an increased inhibitory effect compared to systems of carboxylic acid and alkalis based on sodium hydroxide solution or ammonia.

The DE 102007004325 describes an emulsifier system for the production of coolant emulsions suitable for use in the machining of light metals or aluminum alloyed metals. The emulsifier system comprises a corrosion protection system consisting of light metal inhibitors such as carboxylic acids and phosphonic acids, which in addition to avoid the so-called fountain blacks contains chelating tertiary organic amine compounds having phosphonic acid groups. Furthermore, the corrosion protection system contains alkanolamines, preferably mono- and trialkanolamines, as bases for providing particularly effective inhibiting carboxylic and phosphonic acid salts.

The DE 4444878 discloses a water-soluble inhibitor system based on monocarboxylic acids and aromatic hydroxy compounds with a pK _s value for the Hydroxy group in the range of 7.0 to 11, wherein both components are in a certain weight ratio to each other. The JP2005015617 discloses an aqueous anticorrosion composition for metalworking comprising an aliphatic carboxylic acid in combination with an amine, preferably bis (2-dimethylaminoethyl) ether or N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) , contains. The DE 19747895 discloses a corrosion protection system for the neutral pH range based on a combination of one or more carboxylic acids and one or several nitrogen compounds selected from organic amines or nitrogen-containing heterocycles, wherein the nitrogen compounds have a _pK a value for at least one protolysis stage is in the range 6-9 , wherein both components are in a certain weight ratio to each other. Preferred nitrogen compounds may for example be selected from linear or cyclic alkylenediamines, alkylene triamines and alkylene tetraamines.

The object of the present invention is to provide an aqueous surface-active and corrosion-protective preparation suitable for the production of aqueous metal treatment and metalworking fluids, in particular cleaners and lubricants, that metals, in particular iron and iron alloys, in comparison with the prior art in contact with the Treatment and processing fluid more effectively protects against corrosion.

This object is achieved by an aqueous surface-active and corrosion-protective preparation according to the present claim 1. The inventive aqueous surface-active and corrosion-protective preparation provides excellent protection against corrosion of iron and iron alloys and of aluminum and Aluminum alloys in contact with aqueous liquids, in particular liquids for metal treatment or metalworking. Furthermore, the corrosion protection system (I) is characterized by its good water solubility, which makes it possible to distribute the corrosion protection system in the form of highly concentrated aqueous preparations.

Each preparation, for example a ready-to-use metal treatment or metalworking fluid or its concentrate, which contains the two components a) and b), thus comprises the corrosion protection system (I). Typically, a solution of the anticorrosive system is formulated into a metalworking or metalworking fluid to impart the desired anticorrosive properties. For compatibility with aqueous metal treatment and metalworking fluids according to the invention, corrosion protection systems which store the components a) and b) in an aqueous phase are therefore preferred.

wobei die Reste R₁, R₂, R₃ und R₄ unabhängig voneinander ausgewählt sind aus verzweigten oder unverzweigten Alkylresten mit nicht mehr als 8 Kohlenstoffatomen und -((CH₂)_o-X)_p-R₅, wobei o eine natürliche ganze Zahl im Bereich von 1 bis 3, p eine natürliche ganze Zahl im Bereich von 1 bis 6 ist, X entweder ein Sauerstoff- oder ein Stickstoffatom ist und der Rest R₅ ausgewählt ist aus Wasserstoff, Methyl, Ethyl oder Propyl; mit m und n als natürliche ganze Zahlen im Bereich von 1 bis 3.In a preferred corrosion protection system (I) as component b) at least one amine of the following structural formula (1) is contained:

wherein the radicals R ₁ , R ₂ , R ₃ and R _{4 are} independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms and - ((CH ₂ ) _o -X) _p -R ₅ , where o is a natural whole Number in the range of 1 to 3, p is a natural integer in the range of 1 to 6, X is either an oxygen or a nitrogen atom, and R _{5 is} selected from hydrogen, methyl, ethyl or propyl; with m and n as natural integers in the range of 1 to 3.

wobei die Reste R₁ und R₂ unabhängig voneinander ausgewählt sind aus verzweigten oder unverzweigten Alkylresten mit nicht mehr als 8 Kohlenstoffatomen und -((CH₂)_o-X)_p-R₅, wobei o eine natürliche ganze Zahl im Bereich von 1 bis 3, p eine natürliche ganze Zahl im Bereich von 1 bis 6 ist, X entweder ein Sauerstoff- oder ein Stickstoffatom ist und der Rest R₅ ausgewählt ist aus Wasserstoff, Methyl, Ethyl oder Propyl; mit m und n als natürliche ganze Zahlen im Bereich von 1 bis 3; und wobei q, r und s ganze natürliche Zahlen im Bereich von 1 bis 3 sind und Z entweder ein Kohlenstoff-, Sauerstoff- oder Stickstoffatom ist.Alternatively, the radicals R ₁ , R ₂ , R ₃ and R _{4 of} the structural formula (1) may be selected from those containing the two nitrogen atoms of the oxybis (alkylamine) moiety bridge, so that the radical R ₁ and / or the radical R _{2 are} each structurally identical to the radical R ₃ or R ₄ , wherein bridging radicals R ₁ or R ₂ or R ₃ or R _{4 are} selected from alkylene, polyoxyalkylenes or polyaminoalkylenes with not more than 6 carbon atoms. Such a preferred bridged amine in a corrosion protection system (I) has the following general structural formula (1a):

wherein the radicals R ₁ and R _{2 are} independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms and - ((CH ₂ ) _o -X) _p -R ₅ , where o is a natural integer in the range of 1 to 3, p is a natural integer in the range of 1 to 6, X is either an oxygen or a nitrogen atom, and R _{5 is} selected from hydrogen, methyl, ethyl or propyl; with m and n as natural integers in the range of 1 to 3; and wherein q, r and s are integer numbers in the range of 1 to 3 and Z is either a carbon, oxygen or nitrogen atom.

Particularly preferred are amines of the structural formula (1a) for which the radicals R ₁ and R _{2 are} independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms, preferably not more than 4 carbon atoms, for the m, n, q and r is 2, and s is not greater than 3, where Z is an oxygen or nitrogen atom. Particularly preferred bridged amines are N, N'-dimethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-diethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-dimethyl 1,4,10-trioxa-7,13-diazacyclopentadecane and N, N'-diethyl-1,4,10-trioxa-7,13-diazacyclopentadecane.

Particularly preferably, the radicals R ₁ , R ₂ , R ₃ and R _{4 of} the structural formula (1) are independently selected from branched or unbranched alkyl radicals with no more as 8 carbon atoms, more preferably not more than 4 carbon atoms, wherein the natural integers m and n are equal to 2. Especially preferred are N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) and N, N, N', N'-tetraethyl-2,2'-oxybis (ethylamine).

A preferred corrosion protection system (I) contains at least 50% by weight, more preferably at least 80% by weight, only those organic amines according to component b) which are selected from amines of the general structural formula (1) according to component b) , particularly preferably from such amines of general structural formula (1) according to component b), for which the radicals R ₁ , R ₂ , R ₃ and R _{4 are} independently selected from branched or unbranched alkyl radicals having not more than 4 carbon atom, wherein the natural integers m and n are 2, and more preferably are selected from N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) and / or N, N, N', N '-Tetraethyl-2,2'-oxybis (ethylamine).

The aliphatic carboxylic acids according to component a) of the corrosion protection system (I) having at least 6 but not more than 14 carbon atoms can be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic carboxylic acids, but are preferably selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.

As carboxylic acids according to component a) with inserted into the carbon chain oxygen heteroatoms are preferably selected ether carboxylic acids of the general formula R- (OC ₂ H ₄ ) _n -OCH ₂ COOH, where R is a linear or branched, saturated or unsaturated alkyl radical having 6 to Is 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are to be matched to one another such that the sum of the carbon and oxygen atoms is not greater than 25, neglecting the carboxyl group. The ether carboxylic acids may be technical mixtures of molecules with different radicals R and different values for n. An example of this is the technical Laurylethercarbonsäure, in which R for is a mixture of linear, saturated alkyl groups having 12 and 14 carbon atoms and n is about 2.5.

The aliphatic phosphonic acids having at least 4 but not more than 18 carbon atoms contained in the corrosion protection system (I) according to component a) may be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic phosphonic acids, but are preferably selected from saturated straight-chain or linear branched monophosphonic acids. Mixtures of different acids may be particularly advantageous, the alkyl monophosphonic acids are particularly suitable in their straight-chain form. Further preferred are alkyl monophosphonic acids having 6 to 12 carbon atoms.

The use of carboxylic acids as component a) is always preferable for ecological reasons, if the use of phosphonic acids is not able to significantly improve the temporary corrosion protection in metal treatment or metalworking.

In a preferred embodiment of the corrosion protection system (I), component a) is therefore selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, and / or carboxylic acids with into the carbon chain inserted oxygen heteroatoms having between 6 and 26 atoms in the carbon heteroatom chain, in particular ether carboxylic acids of the general formula R- (OC ₂ H ₄ ) _n -OCH ₂ COOH, wherein R is a linear or branched, saturated or unsaturated alkyl radical 6 to 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are coordinated so that the sum of the C and O atoms is neglecting the carboxyl group is not greater than 25.

In a particularly preferred corrosion protection system (I), component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.

Particularly preferred in this regard is an embodiment of the corrosion protection system in which the weight-based proportion of carboxylic acids according to component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular the weight-related proportion of caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, on the total amount of carboxylic acids and phosphonic acids in the corrosion protection system, including those carboxylic acids and phosphonic acids which are not compounds according to component a), at least 50 wt .-%, particularly preferably at least 80 wt .-% is.

It is known to the person skilled in the art that components a) and b) of the corrosion protection system (I) can undergo acid-base reactions with one another and, in aqueous solution, also have a protolysis equilibrium with their respective deprotonated or protonated form.

It has been found in this context that both the water solubility and the anticorrosive effect are positively influenced by the presence of ammonium salts resulting from the neutralization reaction of components a) and b). According to the invention, therefore, that the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not less than 1: 3 in order to ensure a minimum amount of the amine according to component b) is present in the corrosion protection system as ammonium salt. In particular, this molar ratio is not less than 2: 3. Conversely, the total amount of carboxyl and / or phosphonic acid groups of components a) relative to the proportion of amines according to component b) should not exceed values for which the effectiveness of the corrosion protection is clearly evident decreases. For this purpose, the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not greater than 5: 1, more preferably not greater than 3: 1, particularly preferably not greater than 2: 1.

In particular, the corrosion protection system (I) is suitable to be used in aqueous emulsions, especially in cleaning, anticorrosion and cooling lubricant emulsions, to prevent metal corrosion. An advantage of using a corrosion protection system based on components a) and b) is that for a sufficient corrosion protection, a comparatively small amount of these two active components must be present in the aqueous metal working and metal treatment system.

• c) Ethoxylaten/Propoxylaten von Fettalkoholen mit 8 bis 18 Kohlenstoffatomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten und
• d) Fettalkoholen und/oder Fettalkoholpropoxylaten mit 12 bis 24 C Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder dem Destillationsrückstand dieser Fettalkohole enthält.

The present invention therefore encompasses an aqueous surface-active and corrosion-protecting preparation which, in addition to water and the corrosion protection system described above comprising components a) and b), denotes corrosion protection system (I), the molar ratio of the total amount of carboxyl and / or phosphonic acid Groups of components a) to oxybis (alkylamine) units of at least one amine of component b) is not greater than 5: 1, but not less than 1: 3, an emulsifier system (II) consisting of

• c) ethoxylates / propoxylates of fatty alcohols having 8 to 18 carbon atoms in the alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and
• d) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 C atoms in the alcohol and 0 to 3 propylene oxide units and / or the distillation residue of these fatty alcohols.

In a further aspect, the emulsifier system (II) of the aqueous surface-active and anti-corrosive preparation according to the invention additionally comprises alkoxylated fatty amines as component e) to improve the filterability of emulsions prepared from these preparations. For this purpose, preferably alkoxylated fatty amines consisting of one or more alkoxylated saturated and / or unsaturated aliphatic amines having an aliphatic chain length of at least 8, preferably at least 10 and more preferably at least 12, but not more than 20, preferably not more than 18 and most preferably not used more than 16 carbon atoms. The fatty amines used should be ethoxylated with at least 8, preferably not more than 10, but not more than 16, preferably not more than 14 and most preferably 12 ethylene oxide units. In particular, is suitable for increasing the Filterability of ready-to-use emulsions 12 times ethoxylated cocoamine prepared from these formulations.

The proportion of components a) to e) of the preparation according to the invention for an application-ready anticorrosive cleaner solution is preferably in the range from 0.5 to 10% by weight, the total proportion of components a) and b) of the anticorrosion system (I) preferably being at least 0.1 wt .-% is.

However, the preparation according to the invention can also be a concentrate for the production of anticorrosion cleaner solutions in which the proportion of components a) to e) is preferably in the range from 40 to 95% by weight, the total amount of components a) and b) being of the corrosion protection system (I) in the preparation according to the invention is preferably at least 10 wt .-%.

The aqueous surface-active and corrosion-protective preparation may additionally be admixed with a water component of not more than 60% by weight, so that a total of one oil-containing, water-miscible emulsion concentrate for metalworking, in particular a concentrate for a coolant lubricant or anticorrosion emulsion, realized.

1. i) 2 bis 20 Gew.-% eines Korrosionsschutzsystem (I) bestehend aus
   1. a) zumindest einer aliphatischen Carbonsäure mit zumindest 6, jedoch nicht mehr als 14 Kohlenstoffatomen und/oder zumindest einer Carbonsäure mit in die Kohlenstoffkette eingeschobenen Sauerstoff-Heteroatomen, die zwischen 6 und 26 Atome in der Kohlenstoff-Heteroatomkette aufweist, und/oder zumindest einer aliphatischen Phosphonsäure mit zumindest 4, jedoch nicht mehr als 18 Kohlenstoffatomen,
   2. b) zumindest einem Amin, das zumindest eine Oxybis(alkylamin)-Einheit mit tertiären Amino-Gruppen aufweist, wobei die Alkylketten dieser Einheit jeweils aus nicht mehr als 4 Kohlenstoffatomen bestehen,
   wobei das Gewichtsverhältnis der Komponenten a) und b) von 1 : 0,2 bis 0,3 : 1 variieren kann,
2. ii) 2 bis 50 Gew.-% eines Emulgatorsystems (II) bestehend aus
   • c) Ethoxylaten/Propoxylaten von Fettalkoholen mit 8 bis 18 Kohlenstoffatomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten und
   • d) Fettalkoholen und/oder Fettalkoholpropoxylaten mit 12 bis 24 C Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder dem Destillationsrückstand dieser Fettalkohole,
   wobei das Gewichtsverhältnis der Komponenten c) und d) von 1 : 0,3 bis 0,3 : 1 variieren kann, und
3. iii) 5 bis 50 Gew.-% einer Ölkomponente (III),

und gegebenenfalls weitere Hilfs- und Wirkstoffe (IV), wobei die Summe der Bestandteile I) bis IV) 60 bis 95 Gew.-% ausmacht und der verbleibende Gewichtsanteil Wasser darstellt.The present invention therefore also relates to an oil-containing, water-miscible emulsion concentrate according to the invention

1. i) 2 to 20 wt .-% of a corrosion protection system (I) consisting of
   1. a) at least one aliphatic carboxylic acid having at least 6, but not more than 14 carbon atoms and / or at least one carboxylic acid having inserted into the carbon chain oxygen heteroatoms having between 6 and 26 atoms in the carbon heteroatom chain, and / or at least one aliphatic Phosphonic acid having at least 4 but not more than 18 carbon atoms,
   2. b) at least one amine having at least one oxybis (alkylamine) moiety having tertiary amino groups, wherein the alkyl chains of this moiety each consist of not more than 4 carbon atoms,
   wherein the weight ratio of components a) and b) can vary from 1: 0.2 to 0.3: 1,
2. ii) 2 to 50 wt .-% of an emulsifier system (II) consisting of
   • c) ethoxylates / propoxylates of fatty alcohols having 8 to 18 carbon atoms in the alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and
   • d) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 C atoms in the alcohol and 0 to 3 propylene oxide units and / or the distillation residue of these fatty alcohols,
   wherein the weight ratio of components c) and d) can vary from 1: 0.3 to 0.3: 1, and
3. iii) from 5 to 50% by weight of an oil component (III),

and optionally other excipients and active ingredients (IV), wherein the sum of constituents I) to IV) constitutes 60 to 95% by weight and the remaining weight fraction represents water.

With regard to the corrosion protection system (I) and the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention, the preferred embodiments are identical to those described for the corrosion protection system and the aqueous surface-active and corrosion-protective preparation according to the invention.

In this respect, the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention, as described above for the aqueous surface-active and anti-corrosive preparation, alkoxylated fatty amines as component e), preferably with a weight fraction in the concentrate of at least 1 wt .-%, more preferably at least 2 wt .-%, but preferably not more than 10 wt .-%, particularly preferably not more than 8 wt .-%.

The oil component (III) of the oily, water-miscible emulsion concentrate according to the invention is preferably selected from paraffinic or naphthenic mineral oils, dialkyl ethers having 12 to 20 carbon atoms and / or ester oils.

As optional further auxiliaries or active ingredients may be mentioned: lubricating additives in general and in particular so-called "extreme pressure" additives (so-called EP additives) and biocides in each case in an amount of preferably 0.1 to 2 wt .-% in the concentrate; Buffer systems, in particular based on boric acid, in an amount based on the particular acid form of preferably 2 to 10 wt .-% in the concentrate; Neutralizing agent based on alkanolamines, solubilizers such as glycols, glycerol or sodium cumenesulfonate each in an amount of preferably 1 to 6 wt .-% in the concentrate.

Furthermore, the invention relates to the ready-to-use oil-in-water emulsion which is obtainable by adding from about 0.5 to about 10 parts by weight of the above-described oily, water-miscible concentrate with about 99.5 to about 90 parts by weight of water. Due to the self-emulsifying properties of the emulsion concentrate, the ready-to-use emulsion forms spontaneously upon addition of water or after slight mechanical agitation such as stirring. This emulsion can be used for example as a cleaning, corrosion protection or cooling lubricant emulsion.

The oil-containing, water-miscible emulsion concentrate according to the invention and the ready-to-use oil-in-water emulsions preparable therefrom by dilution with water are particularly suitable for the treatment and processing of iron and iron alloys and of aluminum and aluminum alloys.

In the following, the mode of action of the corrosion protection system (I) is shown by way of example and compared with systems known in the prior art. For this purpose, a corrosion protection test according to DIN 51360-2 is carried out in which gray cast iron chips (type GG25) are wetted on a round filter with freshly prepared dilute aqueous solutions containing various corrosion protection systems based on an amine and isononanoic acid.

Table 1 lists the compositions of concentrated aqueous corrosion protection systems (stock solutions) based on an amine and isononanoic acid. Table 1 Stock solutions of the corrosion protection systems with an active component content of 20% by weight in water with a hardness of 20 ° dH (3.04 mmol CaCl ₂ , 0.54 mmol MgSO ₄ ) Amine component Wt .-% carboxylic acid Wt .-% B1 N, N, N 'N'-tetramethyl-2,2'-oxybis (ethylamine), 10.07 isononanoic 9.93 V1 Monoethanolamine 5.57 isononanoic 14.43 V2 triethanolamine 9.71 isononanoic 10.29 V3 N, N, N ', N'-tetramethyl-1,6-hexamethylenediamine 10.43 isononanoic 9.57

The stock solutions of Table 1 were mixed with water with a hardness of 20 ° dH, further diluted and wets the cast iron chips on the filter paper with this diluted solution (3.04 mM _CaCl2 0.54 mmol MgSO _4).

Table 2 shows the degree of rust formation as a function of the active content of the solutions based on the assessment of the corrosion marks on the filter paper after 2 hours exposure of the chips at 20 ° C.

On the basis of the corrosion results set out in Table 2 it is clear that the corrosion protection system (I) containing the amine with a Oxybis (alkylamine) unit already shows a significant corrosion protection effect from a weight fraction of 6% based on the stock solution B1. At a weight fraction of at least 7% based on the stock solution B1, only slight corrosion phenomena on the filter paper are detectable, while for the other corrosion protection systems a moderate (V3) to further strong (V1, V2) corrosion can be observed. The corrosion protection system (B1) containing the amine with the oxybis (alkylamine) unit is also superior to the corrosion protection system (V3) containing the hexamethylene-bridged tertiary diamine. Tab. 2 Corrosion results in the filter test according to DIN 51 360 of 2 samples each of gray cast iron chips (type GG25), which were brought into contact with differently diluted stock solutions according to Tab Proportion of stock solution in% by weight 5 6 7 8th B1 4.4 3.3 2.1 0/0 V1 4.4 4.4 4.4 2.2 V2 4.4 4.4 4.4 4.4 V3 4.4 4.4 3.3 1.1

• 0 keine Korrosion / unverändert
• 1 Spuren von Korrosion / höchstens 3 Korrosionsabzeichnungen
• 2 leichte Korrosion / nicht mehr als 1 % der Oberfläche verfärbt
• 3 mäßige Korrosion / nicht mehr als 5% der Oberfläche verfärbt
• 4 starke Korrosion / über 5% der Oberfläche verfärbt

Assessment of corrosion according to DIN 51 360:

• 0 no corrosion / unchanged
• 1 traces of corrosion / maximum of 3 corrosion marks
• 2 slight corrosion / not more than 1% of the surface discolored
• 3 moderate corrosion / not more than 5% of the surface discolored
• 4 strong corrosion / over 5% of the surface discolored

Claims (8)

1. An aqueous, surface-active and anti-corrosion preparation containing, in addition to water,

   i) a corrosion protection system (I) comprising

   a) aliphatic carboxylic acids having at least 6 but no more than 14 carbon atoms and/or carboxylic acids having oxygen heteroatoms inserted in the carbon chain, which have between 6 and 26 atoms in the carbon heteroatom chain, and/or aliphatic phosphonic acids having at least 4 but no more than 18 carbon atoms,

   b) at least one amine which has at least one oxybis(alkylamine) unit having tertiary amino groups, wherein the alkyl chains of this unit each consist of no more than 4 carbon atoms, wherein the molar ratio of the total amount of carboxyl acid groups and/or phosphonic acid groups of components a) to oxybis(alkylamine) units of the at least one amine of component b) is no greater than 5:1 but no smaller than 1:3,

   ii) an emulsifier system (II) consisting of

   c) ethoxylates/propoxylates of fatty alcohols having from 8 to 18 carbon atoms in the alcohol having from 2 to 6 ethylene oxide units and from 4 to 8 propylene oxide units and

   d) fatty alcohols and/or fatty alcohol propoxylates having from 12 to 24 C atoms in the alcohol and from 0 to 3 propylene oxide units and/or the distillation residue of these fatty alcohols.
2. The preparation according to claim 1, characterized in that the molar ratio of the total amount of carboxyl acid groups and/or phosphonic acid groups of components a) to oxybis(alkylamine) units of the at least one amine of component b) of the relevant corrosion protection system (I) is no greater than 3:1 but no smaller than 2:3.
3. The preparation according to one or both of the preceding claims, characterized in that at least one amine of the following structural formula (1) is contained as component b) of the corrosion protection system (I):

   

   the functional groups R₁, R₂, R₃ and R₄ being selected, independently of one another, from branched or unbranched alkyl functional groups having no more than 8 carbon atoms and - ((CH₂)_x-O)_y-R₅, where x is a natural integer in the range of from 1 to 3, y is a natural integer in the range of from 1 to 6 and the functional group R₅ is selected from hydrogen, methyl, ethyl or propyl;
   and/or the functional groups R₁, R₂, R₃ and R₄ being selected from functional groups of this kind which bridge the two nitrogen atoms of the oxybis(alkylamine) unit such that the functional group R₁ and/or the functional group R₂ are each structurally identical to the functional group R₃ or R₄, bridging functional groups R₁ or R₂ and R₃ or R₄ being selected from alkylenes, polyoxyalkylenes or polyaminoalkylenes having no more than 6 carbon atoms; where m and n are natural integers in the range of from 1 to 3.
4. The preparation according to claim 3, characterized in that at least one amine of structural formula (1) is contained as component b) of the corrosion protection system (I), functional groups R₁, R₂, R₃ and R₄ being selected, independently of one another, from branched or unbranched alkyl functional groups having no more than 8, preferably no more than 4, carbon atoms, and the natural integers m and n being equal to 2.
5. The preparation according to one or more of the preceding claims, characterized in that, based on the total proportion of the amines according to component b) of the corrosion protection system (I), at least 50 wt.%, preferably at least 80 wt.%, of the amines of component b) of the corrosion protection system (I) are selected from amines of structural formula (I) according to one of claims 3 or 4.
6. The preparation according to one or more of the preceding claims, characterized in that component a) of the corrosion protection system (I) is selected from aliphatic branched or unbranched monocarboxylic acids, which are preferably selected from caprylic acid, ethylhexanoic acid, isononanoic acid and isodecanoic acid.
7. An oil-containing, water-miscible emulsion concentrate containing

   i) from 2 to 20 wt.% of a corrosion protection system (I) comprising

   a) aliphatic carboxylic acids having at least 6 but no more than 14 carbon atoms and/or carboxylic acids having oxygen heteroatoms inserted in the carbon chain, which have between 6 and 26 atoms in the carbon heteroatom chain, and/or aliphatic phosphonic acids having at least 4 but no more than 18 carbon atoms,

   b) at least one amine which has at least one oxybis(alkylamine) unit having tertiary amino groups, wherein the alkyl chains of this unit each consist of no more than 4 carbon atoms, wherein the weight ratio of components a) and b) can vary from 1:0.2 to 0.3:1

   ii) from 2 to 50 wt. % of an emulsifier system (II) consisting of

   c) ethoxylates/propoxylates of fatty alcohols having from 8 to 18 carbon atoms in the alcohol having from 2 to 6 ethylene oxide units and from 4 to 8 propylene oxide units and

   d) fatty alcohols and/or fatty alcohol propoxylates having from 12 to 24 carbon atoms in the alcohol and from 0 to 3 propylene oxide units and/or the distillation residue of these fatty alcohols, wherein the weight ratio of components c) and d) can vary from 1:0.3 to 0.3:1, and

   iii) from 5 to 50 wt.% of an oil component (III), and optionally further auxiliary agents and active ingredients (IV), wherein the sum of the constituents I) to IV) makes up from 60 to 95 wt.% and the remaining weight proportion is water.
8. The oil-containing, water-miscible emulsion concentrate according to claim 7, characterized in that paraffinic or naphthenic mineral oils, dialkyl ethers having from 12 to 20 carbon atoms and/or ester oils are used as the oil component (III).