DE102007004325A1 - Cooling lubricant for the aqueous machining of aluminum-alloyed magnesium - Google Patents

Abstract

The present invention relates to an oil-containing, water-miscible emulsion concentrate containing (I) an oil component, (II) an emulsifier system comprising a) 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 b) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 carbon atoms in the alcohol and 0 to 3 propylene units and / or the distillation residue of these fatty alcohols, and (III) a corrosion protection system comprising a) straight-chain and / or branched carboxylic acids and / or phosphonic acids with 6 to 12 carbon atoms, characterized in that the corrosion protection system (III) additionally contains chelating organic amine compounds (IIIb) with one or more tertiary nitrogen atom (s) whose organic radicals functional groups, X) <SUB> 2 </ SUB >, -PH (= O) OX, -COOX, and / or represent an aliphatic group with not more than 4 C atoms, wherein the organic Residues of compounds (IIIb) having terminal tertiary-substituted nitrogen atoms or the organic radicals of compounds (IIIb) having only one tertiary-substituted nitrogen atom, at least two functional groups selected from -OP (= O) (OX) <SUB> 2 </ SUB> , -P (= O) (OX) <SUB> 2 </ SUB> and / or -PH (= O) OX, and X is a hydrogen atom, an alkali metal cation, an ammonium ion, a quaternary ammonium compound and / or an aliphatic residue with no more ...

Description

The The invention relates to an oily, water-miscible emulsion concentrate for the production of low-foaming oil-in-water emulsions, This applies to different technical metalworking processes in soft and hard water as cleaning, anti-corrosive or cooling lubricant emulsions of light metals, in particular Aluminum and its alloys and aluminum-alloyed magnesium suitable. The emulsifier system therefore 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 black caused by the Corrosion of magnesium workpiece chelating organic Contains amine compounds. Furthermore, the invention relates from the oil-containing, water-miscible emulsion concentrate prepared ready-to-use oil-in-water emulsions. The emulsions are also at higher water hardnesses stable and have the added benefit of being the Water hardness (calcium carbonate) and the increased Metal salt freight (corrosion products) dispersed or in solution in complexed form.

Corrosion protection emulsions are used as passivation agents for the temporary protection of metallic workpieces against atmospheric, corrosion-causing influences used. They contain essentially non-polar or polar oils, Emulsifiers, corrosion inhibitors and water. commercial Systems based on oil concentrates, emulsifiers and Corrosion inhibitors, but little or no water included. The emulsifiers and corrosion inhibitors used must therefore be oil-soluble. For the production of oil-in-water emulsions ("O / W emulsions"), which are incorporated in US Pat diluted with water must be used Such systems should be self-emulsifying.

Coolant emulsions in the non-cutting or machining of metallic Workpieces are used, have a similar Composition like anti-corrosive emulsions, as they also have to show a corrosion-inhibiting effect. By Addition of suitable lubricating additives allows the lubricating effect improve.

all These emulsion types have in common that they because of the used emulsifiers tend to foam. The foam tendency is particularly pronounced when the emulsifier anionic Contains surfactants. When used in hard water is the Foam tendency is reduced by the fact that the anionic surfactants can form sparingly soluble salts with calcium ions, the foam-inhibiting effect. In soft to medium-hard water, so in water with less than 12 ° dH and in particular with less than 8 ° dH, such emulsions are because of the high foaming tendency at least not usable if worked by spraying becomes.

• a) Ethoxylaten/Propoxylaten von Fettalkoholen mit 8 bis 18 C-Atomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten,
• b) Fettalkoholen und/oder Fettalkoholpropoxylaten mit 12 bis 24 C-Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder Destillationsrückstand dieser Fettalkohole und
• c) Ethercarbonsäuren der allgemeinen Formel (I) oder deren Anionen,

R-O-(CHA-CH₂O)_n-(CH₂)_m-COOH (I) wobei R für einen gesättigten oder ungesättigten, linearen oder verzweigten Alkylrest mit 5 bis 22 C-Atomen,
A für Wasserstoff oder eine Methylgruppe,
n für eine Zahl im Bereich von 1,5 bis 15 und
m für eine ganze Zahl im Bereich von 1 bis 3 steht
im Gewichtsverhältnis a:b:c = 1:0,3:0,1 bis 1:4:1.The DE-A-19956237 discloses a low-foaming emulsifier system which can be used in both soft and hard water and has sufficient stability, especially at high water hardness, consisting of

• a) ethoxylates / propoxylates of fatty alcohols having 8 to 18 C atoms in the alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units,
• b) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 carbon atoms in the alcohol and 0 to 3 propylene oxide units and / or distillation residue of these fatty alcohols and
• c) ether carboxylic acids of the general formula (I) or their anions,

RO- (CHA-CH ₂ O) _n - (CH _{2) m} -COOH (I) where R is a saturated or unsaturated, linear or branched alkyl radical having 5 to 22 C atoms,
A is hydrogen or a methyl group,
n for a number in the range of 1.5 to 15 and
m is an integer in the range of 1 to 3
in weight ratio a: b: c = 1: 0.3: 0.1 to 1: 4: 1.

Furthermore, the doctrine of DE-A-19956237 show that the corrosion protection system of the emulsion concentrate in addition to the typically used carboxylic acids for the treatment of light metals such as aluminum and magnesium and their alloys must preferably contain alkylphosphonic with 4 to 18 carbon atoms in order to significantly reduce the corrosive dissolution of the metallic workpiece. The suppression of corrosion and thus especially in the machining of base metali The inevitable occurrence of hydrogen evolution is also of great importance for safety and procedural reasons.

One increased entry of metal salts in the emulsion in the Processing of base metals such as aluminum and magnesium and their alloys due to corrosion of the workpiece conditions that the emulsion used a very high dispersibility must own. Good filterability of the emulsion, in particular in the machining of metal workpieces procedurally necessary, must also for an increased metal salt load may be present in the emulsion. Usually The emulsion is in a cooling lubricant system during the metalworking process via a fine filtration with a pore size smaller than 50 μm by means of high-pressure pumps (> 200 Bar) in the circuit, so that the filter system through the precipitation of dissolved metal salts at inadequate Dispersibility of the emulsion is overloaded. Premature overloading of the fine filtration plant in the so-called care level of the cooling lubricant circuit is for procedural reasons and because of the high costs incurred for the use of new fine filters or however, avoid their reprocessing.

Of Another is a pH increase of the coolant lubricant emulsion due to corrosion of the workpiece during machining critical for stability and dispersibility the oil-in-water emulsion. A high alkalinity The emulsions used can also lead to a significant Entlackung and thus to an increased corrosion of the metalworking Lead process used lacquer coated tools, so that their life is significantly reduced. Not least means a significant pH increase in the application solution to pH values above pH 10 also an additional hazard for directly active in metalworking Persons due to acute skin irritation and chronic skin damage, which are to be avoided for reasons of occupational safety.

In spite of the extensive developments of the past years in the field the oily, water - miscible emulsion concentrates for Metalworking, it has not been successful, corrosion protection systems to formulate for oil-in-water emulsions adequately satisfy the above criteria and also the occurrence of temper colors of the so-called "fountain blacks", which is a dark color of the aqueous emulsion in contact aluminum-containing metallic materials, largely prevent. This "fountain black" represents an undesirable, since largely irreversible discoloration the material surface, which is caused by superficial Pickling operations typically in the processing of aluminum, Aluminum alloys and aluminum alloyed metals in aqueous Systems occurs.

The Invention is therefore the object of an oily, water-miscible emulsion concentrate suitable for different technical metalworking processes in soft and in hard water as a cleaning, corrosion protection or cooling lubricant emulsion for aluminum, aluminum alloys and / or aluminum alloys Metals, preferably aluminum-alloyed magnesium, being suitable the appearance of the so-called "fountain blacks" of the metallic material during the machining process omitted.

• (I) eine Ölkomponente
• (II) ein Emulgatorsystem enthaltend a) Ethoxylate/Propoxylate von Fettalkoholen mit 8 bis 18 C-Atomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten und b) Fettalkohole und/oder Fettalkoholpropoxylate mit 12 bis 24 C-Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder dem Destillationsrückstand dieser Fettalkohole und
• (III) ein Korrosionsschutzsystem enthaltend a) geradkettige und/oder verzweigte Carbonsäuren und/oder Phosphonsäuren mit 6 bis 12 C-Atomen,

dadurch gekennzeichnet, dass das Korrosionsschutzsystem (III) zusätzlich chelatbildende organische Aminverbindungen (III b) mit einem oder mehreren tertiären Stickstoffatomen enthält, deren organische Reste funktionale Gruppen ausgewählt aus -O-P(=O)(OX)₂, -P(=O)(OX)₂, -PH(=O)OX, -COOX aufweisen und/oder eine aliphatische Gruppe mit nicht mehr als 4 C-Atomen darstellen, wobei die Reste von Verbindungen (III b) mit endständigen tertiär substituierten Stickstoffatomen oder die Reste von Verbindungen (III b) mit nur einem tertiär substituierten Stickstoffatom mindestens zwei funktionale Gruppen ausgewählt aus -O-P(=O)(OX)₂, -P(=O)(OX)₂ und/oder -PH(=O)OX enthalten, und X ein Wasserstoffatom, ein Alkalimetall-Kation, ein Ammonium-Ion, eine quarternäre Ammoniumverbindung und/oder ein aliphatischer Rest mit nicht mehr als 4 C-Atomen ist.This object is achieved by an oily, water-miscible emulsion concentrate containing

• (I) an oil component
• (II) an emulsifier system containing a) 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 b) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 carbon atoms in the alcohol and 0 to 3 propylene oxide units and / or the distillation residue of these fatty alcohols and
• (III) a corrosion protection system comprising a) straight-chain and / or branched carboxylic acids and / or phosphonic acids having 6 to 12 C atoms,

characterized in that the corrosion protection system (III) additionally contains chelating organic amine compounds (III b) having one or more tertiary nitrogen atoms whose organic radicals have functional groups selected from -OP (= O) (OX) ₂ , -P (= O) ( OX) ₂ , -PH (= O) OX, -COOX and / or an aliphatic group having not more than 4 C atoms, wherein the residues of compounds (III b) with terminal tertiary substituted nitrogen atoms or the residues of compounds (III b) containing only one tertiary-substituted nitrogen atom containing at least two functional groups selected from -OP (= O) (OX) ₂ , -P (= O) (OX) ₂ and / or -PH (= O) OX, and X is a hydrogen atom, an alkali metal cation, an ammonium ion, a quaternary ammonium compound and / or an aliphatic radical having not more than 4 C-Ato men is.

wobei der organische Substituent Y mindestens eine funktionale Gruppe ausgewählt aus -O-P(=O)(OX)₂, -P(=O)(OX)₂, -PH(=O)OX, -COOX enthält und/oder einer aliphatischen Gruppe mit nicht mehr als 4 C-Atomen entspricht und der organische Substituent Z mindestens eine funktionale Gruppe ausgewählt aus -O-P(=O)(OX)₂, -P(=O)(OX)₂, -PH(=O)OX enthält und bei der die Reste R¹ und R² unabhängig voneinander und unabhängig von den x konstituierenden Einheiten (CR¹R²) Wasserstoffatome, aliphatische Reste mit nicht mehr als 4 C-Atomen oder Substituenten Y sind, x mindestens 1 und höchstens 4 ist und n mindestens 2 beträgt.Furthermore, preference is given to chelating organic amine compounds (IIIb) in the oil-containing, water-miscible emulsion concentrate which correspond to the general structural formula (A),

wherein the organic substituent Y contains at least one functional group selected from -OP (= O) (OX) ₂ , -P (= O) (OX) ₂ , -PH (= O) OX, -COOX and / or an aliphatic group with no more than 4 carbon atoms and the organic substituent Z contains at least one functional group selected from -OP (= O) (OX) ₂ , -P (= O) (OX) ₂ , -PH (= O) OX and in which the radicals R ¹ and R ² independently of one another and independently of the x constituent units (CR ¹ R ² ) are hydrogen atoms, aliphatic radicals having not more than 4 C atoms or substituents Y, x is at least 1 and at most 4 and n is at least 2.

It proves to be advantageous if the corrosion protection system of the oil-containing, water-miscible emulsion concentrate contains such chelating organic amine compounds (III b) according to the abovementioned definition whose functional groups -OP (OO) (OX) ₂ , -P (OO) (OX ) ₂ , -PH (= O) OX, -COOX in each case and independently of one another in α, β or γ position to the tertiary nitrogen atom.

Surprisingly So it turns out that the inhibition of the aluminum or aluminum alloy surface depends essentially on the same factors, which also provides optimal complexation of the dissolved metal cations condition the machined workpiece, namely the possibility of forming 5-, 6- or 7-membered Chelate.

wobei n mindestens 1, aber nicht größer als 8 und vorzugsweise 3 ist, und die Substituenten X unabhängig voneinander ausgewählt sind aus Wasserstoffatomen, Alkalimetall-Kationen, Ammonium-Ionen, quarternären Ammoniumverbindungen oder aliphatischen Resten mit nicht mehr als 4 C-Atomen, vorzugsweise aus Wasserstoffatomen und Alkalimetall-Kationen.As in the context of the present invention, and thus to prevent the "fountain black" in metalworking particularly suitable in the emulsion concentrate chelating organic amine compounds prove (III b) according to the general structural formula (B),

wherein n is at least 1, but not greater than 8 and preferably 3, and the substituents X are independently selected from hydrogen atoms, alkali metal cations, ammonium ions, quaternary ammonium compounds or aliphatic radicals having not more than 4 carbon atoms, preferably from Hydrogen atoms and alkali metal cations.

For this belong as explicit representatives of this class of compounds Nitrilotris (methylenephosphonic acid), ethylenediamine tetrakis (methylenephosphonic acid), Diethylenetriaminepentakis- (methylenephosphonic acid), triethylenetetraminehexakis- (methylenephosphonic acid), Tetraethylenepentamine heptakis (methylenephosphonic acid), Pentaethylenehexamine-oktakis- (methylenephosphonic acid), hexaethyleneheptamine-nonakis- (methylenephosphonic acid) and heptaethylene octamine decakis (methylenephosphonic acid) and their partially and completely neutralized sodium salts.

The chelate-forming amine compounds (III b) should be present in the emulsion concentrate in concentrations which, on the one hand, have an inhibiting effect on the discoloration of the material to be processed and, on the other hand, are still acceptable for reasons of economy. The lower concentration limit at which just a positive effect of the inhibitor according to the invention is detectable, is given by about 0.05 wt .-% of the chelating amine compounds (III b) on the emulsion concentrate. As the proportion of inhibitor increases, the performance, ie the suppression of "fountain blacks", becomes more significant, with a maximum performance of about 0.5% by weight be because the application solution during operation of a cooling lubricant system to inhibitors due to their pronounced affinity for the metal surface is continuously depleted. In the context of this invention, the upper limit for the proportion of chelating amine compounds (III b) for efficiency and cost reasons is about 2 wt .-% of the emulsion concentrate.

• i) 5 bis 50 Gew.-% der Ölkomponente (I),
• ii) 2 bis 50 Gew.-% des Emulgatorsystems (II), enthaltend die Komponenten II a bis II b, wobei das Gewichtsverhältnis der Komponenten a:b von 1:0,3 bis 0,3:1 variieren kann,
• iii) 2 bis 15 Gew.-% des Korrosionsschutzsystems (III), wobei der Gewichtsanteil der chelatbildenden organischen Aminverbindung (III b) am Emulsionskonzentrat zwischen 0,05 und 2 Gew.-% variieren kann,

und gegebenenfalls weitere Hilfs- und Wirkstoffe (IV) enthalten, wobei die Summe der Bestandteile I) bis IV) 60 bis 95 Gew.-% ausmacht und der verbleibende Gewichtsanteil Wasser darstellt.The proportion of the oil component (I), the emulsifier system (II) and the corrosion protection system (III) on the oil-containing, water-miscible emulsion concentrate is variable depending on the type of metal working, the object underlying the invention of emulsion concentrates is solved

• i) from 5 to 50% by weight of the oil component (I),
• ii) from 2 to 50% by weight of the emulsifier system (II) containing the components II a to II b, wherein the weight ratio of the components a: b can vary from 1: 0.3 to 0.3: 1,
• iii) from 2 to 15% by weight of the corrosion protection system (III), where the weight fraction of the chelating organic amine compound (III b) on the emulsion concentrate can vary between 0.05 and 2% by weight,

and optionally further excipients and active ingredients (IV), the sum of constituents I) to IV) being from 60 to 95% by weight and the remaining weight fraction being water.

The composition of the emulsifier system (II) and the molecular structure of the emulsifiers used therefore have to meet strict requirements. Firstly, according to (II a), fatty alcohol ethoxylates / propoxylates must be present which carry both 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units. These more hydrophilic components are to be combined with the more hydrophobic components (IIb) unalkoxylated fatty alcohols having 12 to 24 carbon atoms, their distillation residue or their alkoxylation with up to an average of at most 3 propylene oxide units. Furthermore, the stated approximate weight ratio is to be observed. Distillation residue of fatty alcohols having 12 to 24 carbon atoms by Cognis Germany GmbH & Co. KG, Dusseldorf, sold under the name Pernil ^® RU.

In Another aspect of this invention includes the emulsifier system (II) the oily, water-miscible emulsion concentrate to improve the filterability of the emulsion in addition alkoxylated fatty amines (II c) with a weight fraction of the emulsion concentrate of at least 1% by weight, preferably at least 2% by weight, but not more than 10% by weight, preferably not more than 8% by weight.

Therefor are preferably alkoxylated fatty amines consisting of one or several 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 more preferably not more than 16 carbon atoms used.

The fatty amines used should be at least 8, preferably with at least 10, but not more than 16, preferably not with more than 14, and more preferably 12 ethylene oxide units be ethoxylated.

Especially is suitable for increasing the filterability of the ready-to-use Emulsion as an additional component of the emulsion concentrate 12-fold ethoxylated cocoamine.

In a preferred embodiment, emulsion concentrates which form low-foam emulsions as aqueous application solution largely independently of the water hardness are accessible in that the emulsifier system (II) additionally contains ether carboxylic acids (II d) or their anions of the general formula (B), RO- (CHA-CH ₂ -O) _n - (CH ₂ ) _m -COOH (B) where R is a saturated or unsaturated, linear or branched alkyl radical having 5 to 22 C atoms,
A is hydrogen or a methyl group,
n for a number in the range of 1 to 15 and
m is a number in the range of 1 to 3,
and wherein the weight ratio a: b: d of the constituents of the emulsifier system (II) except for the ethoxylated fatty amines (II c) is between 1: 0.3: 0.1 and 1: 4: 1, particularly preferably in the range of 1: 1 : 0.1 to 1: 3: 0.5.

A in the general formula (B) is preferably hydrogen, ie, the ether carboxylic acids of the general formula (B) preferably contain ethylene oxide groups. m is preferably 1, ie the ether carbon acids are preferably acetyl-terminated.

The Ethercarbonsäuren the general formula (B) can On the other hand, it has a very different structure. For example, can they are ether carboxylic acids derived from a fatty alcohol mixture with 12 to 14 carbon atoms in the alkyl group are derived with ethoxylated on average 2.5 ethylene oxide units and then Acetyl-terminated. For example, acetyl termination can be by reaction of the fatty alcohol ethoxylates with chloroacetic acid respectively. Such products are commercially available. Further examples of useful ether carboxylic acids are acetyl-terminated Ethercarbonsäuren of oleyl alcohol, the average with 9 Ethylene oxide units was ethoxylated by caprylic alcohol, the im Ethoxylated with 8 ethylene oxide units or hexyl alcohol, which was ethoxylated on average with 6 ethylene oxide units. These ether carboxylic acids can each individually, but also in a mixture be used together. In the latter case relate the amounts of the ether carboxylic acid on the mixture of these acids. In this case, the ether carboxylic acids as such or in the form of their alkali metal salts, for example the sodium salts.

The contained in the corrosion protection system (III) of the emulsion concentrate corrosion-inhibiting carboxylic acids and / or phosphonic acids (III a) can be straight-chain or branched. Mixtures of different Acids can be particularly advantageous, wherein the alkylphosphonic acids especially in their straight chain Shape are suitable. Further preferred are alkylphosphonic acids with 4 to 18 C atoms, particularly preferably with 6 to 12 C atoms, or in each case their salts in an amount of 0.1 to 4, preferably from 0.2 to 2 parts by weight of the emulsion concentrate. Especially suitable examples of carboxylic acids are caprylic acid, Ethylhexanoic acid, isononanoic acid and isodecanoic acid.

There Anti-corrosive emulsions usually neutral to basic Having pH values, it is preferable to use the acid groups containing at least partially in neutralized inhibitors Form, so as salts to use. As a basic component for neutralization In particular, potassium hydroxide and / or alkanolamines are suitable, wherein the latter reinforce the corrosion inhibitor effect. Because of the danger of nitrosamine formation is the use of dialkanolamines less preferred. Instead, you use monoalkanolamines or Trialkanolamine or preferably mixtures thereof. Especially ethanolamines are used.

Should the oily, water-miscible emulsion concentrate in addition for emulsions for the treatment of non-ferrous metals such as Be suitable for copper, bronze or brass, so that contains Corrosion protection system (III) additionally preferably non-ferrous metal inhibitors. These can be selected from the group of Triazoles, in particular from benzotriazoles and tolyltriazoles. The Emulsion concentrate then preferably contains about 0.1 up to 1 part by weight of non-ferrous metal inhibitors.

The The emulsion concentrate according to the invention can by Addition of the corresponding parts by weight of an oil component to the anticorrosive and emulsifier system described above to be obtained. Of course it is possible to produce such a concentrate by adding the oil component (I), the individual emulsifiers of the emulsifier system (II) and the Components of the corrosion protection system (III) in any order mixed together. You can see the components (III a-III b) use the corrosion protection system directly as salts. process engineering it is more advantageous, however, the compounds (III a-III b) containing acidic groups, as such, the other Blend components and only after mixing with the oil component and the emulsifier system by adding alkali metal hydroxide, in particular of potassium hydroxide, and / or alkanolamines.

As an oil component (I) can be non-polar or polar petrochemical oils or native origin (= based on vegetable or animal oils or fats). Furthermore, synthetic oil components suitable. Examples of usable oil components are paraffinic or naphthenic mineral oil, dialkyl ethers of 12 to 20 C atoms and / or ester oils.

Especially preferred are emulsion concentrates according to the invention, which have a significant buffering capacity to the pH also at the increased hydrogen evolution, which at the Machining of light metals such as magnesium and / or aluminum alloys even in the presence of the corrosion protection system is not complete can be suppressed, permanently stable. For this In particular, boric acid-containing emulsion concentrates are suitable and as already mentioned concentrates the alkanolamines as pH-stabilizing organic compound class included.

In a particular embodiment, the oily, water-miscible emulsion concentrate therefore as auxiliary and active ingredient (IV) a boric acid / borate-based buffer system, preferably in an amount based on the equivalent amount of boric acid of from 2 to 10 parts by weight of the emulsion concentrate.

For an increased buffering effect and as already mentioned to neutralize the acid contained in the corrosion protection system reacting components, the emulsion concentrate as another Auxiliary and active ingredient (IV) triethanolamine, preferably in an amount of 1 to 6 parts by weight of the emulsion concentrate.

When optional additional auxiliaries or active ingredients may be mentioned: Lubricating additives in general and in particular so-called "extreme pressure" additives (so-called EP additives), preservatives, solubilizers such as glycols, glycerol or sodium cumenesulfonate. Farther can biocides such as 3,3'-Methylenebis (5-methyl-1,3-oxazolidine) and / or iodo-2-propynyl-N-butylcarbamate, which are the Extend the service life of the emulsion.

Of the Weight fraction of the components of the emulsion concentrate used in this Meaning auxiliaries or active substances in the emulsion concentrate, is at least 0.1 weight and is not greater than 2 parts by weight.

Indeed The weight fraction of the solubilizer should be glycerol on the emulsion concentrate at least 1, but 6 parts by weight do not exceed.

About that In addition, the present invention relates to the ready-to-use oil-in-water Emulsion obtainable by mixing from about 0.5 to 10 Parts by weight of an oil-containing, water-miscible emulsion concentrate with about 99.5 to 90 parts by weight of water. Due to the self-emulsifying Properties of the emulsion concentrate forms the ready-to-use Emulsion when mixed with water spontaneously or after minor mechanical movement such as stirring. These Emulsion can be used, for example, as a cleaning, anticorrosion or cooling lubricant emulsion can be used. The emulsions can be used with water of any hardness be, d. H. both with soft water with a hardness below 8 ° dH or even below 4 ° dH, without significant foaming occurs, but also in medium-hard or hard water, d. H. in water with a hardness above 8 ° dH, above 12 ° dH and even in the range of 30 to 40 ° dH without affecting the stability the emulsion is lost. The emulsions are sufficiently low-foaming, to be sprayed at any temperature. she also show the required long-term stability.

Of the pH of the ready-to-use oil-in-water emulsion prepared in this manner is not greater than 10, preferably not larger as 9.5 and not smaller than 8, preferably not smaller than 8.5. Will the buffered borsäurehaltige emulsion concentrate remains used to formulate the application solution the pH in the above-mentioned preferred range even at long Metal working times and a long service life of the emulsion stable.

Oil-in-water emulsions of the emulsion concentrate according to the invention are suitable excellently as cooling lubricant emulsion in the Machining of light metals, in particular of aluminum and its alloys, and more preferably aluminum-alloyed ones Magnesium. To emphasize here is the low tendency to training the "fountain black" of machined with such emulsions aluminous materials conveyed by the presence of the Chelating amine compounds of the invention (III b) and the high dispersibility and the corresponding good filterability with the addition of alkoxylated fatty amines (II c).

Also in the machining of non-ferrous metals, in particular of copper and its alloys, for example brass or bronze, or of material surfaces which are at least partially non-ferrous metal surfaces can represent such oil-in-water emulsions used, as far as they are mentioned above Contain non-ferrous metal inhibitors.

such Emulsions have the advantage of being for processing of components from virtually all of the equipment and vehicle occurring metals and metal alloys are suitable. Therefore When processing different types of metal, the emulsion must be not to be changed.

embodiments

From Table 1 is an exemplary base recipe of an emulsion concentrate according to the Basic lying invention divided according to oil components (I), Emulsifier system (II), corrosion protection system (III) and auxiliaries and active ingredients (IV) refer, wherein the inventive chelating organic amine compounds (III b) are not included. The composition according to Table 1 is therefore to be understood as a base formulation to which the corresponding components (IIIb) are added in the respectively indicated amounts for the other examples according to the invention.

For the production of appropriate application solutions so Inventive oil-in-water emulsions each 50 g of the emulsion concentrate, which is a chelating Organic amine compound (IIIb) with a weight fraction of 0.5% contains on the emulsion concentrate according to Table 1, with water of hardness 20 ° dH (DIN 51360) up to a total amount of application solution of 1000 g offset.

Water according to DIN 51360 is prepared in the following way: A solution A is prepared by dissolving 39 g of calcium chloride hexahydrate with demineralized water to a volume of one liter. Furthermore, a solution B is prepared by dissolving 44 g of magnesium sulfate heptahydrate with demineralized water to a volume of one liter. Take 17 ml of solution A and 3 ml of solution B and add 980 ml of demineralized water. Table 1: Exemplary composition of the basis of an emulsion concentrate to which the chelating amine compound according to the invention according to Table 2 is admixed. system component component Percentage / wt .-% _I oil component White oil 9 Rape 5 _II emulsifier system Fatty alcohol C16-C18, unsaturated fatty alcohol C18; IZ ≤ 95 12.5 alkoxylated (3 EO + 6 PO) fatty alcohol C12-C14 9 ethoxylated (10 EO) oleyl alcohol 6 propoxylated (2 PO) oleyl cetyl alcohol 5 Oleth-10, capryleth-9, hexeth-4-carboxylic acids 1.8 III corrosion protection system isononanoic 6.5 caprylic 6.5 1,2,3-benzotriazole 0.2 IV excipients glycerin 4.5 3,3'-methylenebis (5-methyl-1,3-oxazolidine) 1.8 Iodo-2-propynyl-N-butyl carbamate 0.2 Foam Ban ^® 3529B siloxane-glycol copolymer, polyglycol, polyalkylene glycol mixture 0.1 buffer system potassium hydroxide 6 triethanolamine 4.1 boric acid 4 Aqueous system deionized water ad 100 IZ: iodine value according to DIN ISO 3961: 1996 EO / PO: ethylene oxide or propylene oxide units

Table 2 now indicates the exemplary inventive chelating amine compounds (B1-B4) contained in the emulsion concentrate and the light metal inhibitors used in the comparative examples (V1-V3) in the concentrate. To assess the effectiveness of the particular inhibitor with respect to the suppression of the so-called "fountain blacks" of aluminum-containing materials in contact with the oil-in-water emulsion, 5% by weight of application solutions starting from the emulsion concentrate according to Table 1 are prepared in DIN 51360-water , wherein the emulsion concentrate additionally contains the particular inhibitor with a weight fraction of 0.5% by weight. The composition according to Table 1 is therefore to be understood as a base formulation, which for the further examples according to the invention is the corresponding formula Components (III b) and the light metal inhibitors (V1-V3) used for a comparative consideration in the respective amounts specified.

Then aluminum-alloyed magnesium sheets (AZ91) are immersed in half in these 5 wt .-% use solutions of the emulsion concentrates with the respective inhibitors. Table 3 documents the occurrence of the so-called "well blackened" after a short exposure time t _A and indicates the maximum exposure time t _E after which the respective maximum observed blackening occurs.The evaluation of the "fountain black" takes place on an empirical scale from 0 to 5, which grades the progression of discoloration of the workpiece technically relevant:
0 no discoloration
1 discoloration of the cut surfaces
2 slight discoloration of the outside immediately at the dip limit
3 discoloration of the immersed outside
4 Discoloration of the immersed outside and the cut surfaces
5 strong discoloration of the entire immersed sheet surface

table 3 clearly shows that the chelating agents according to the invention Amine compounds (III b) over the inhibitor-free oil-in-water Emulsion (BV1) the appearance of the "fountain black" delay significantly (B1) or even almost completely suppress (B2-B4). The invention Although tertiary amine B1 prevents rapid discoloration the magnesium alloy, however, indicates the plate after 24 h exposure time a "fountain black" on, which also in the inhibitor-free Application solution is detected.

B1 is therefore only conditionally and exclusively for short machining processes and can be combined with the inhibitors V1 and V2, z. As the typical light metal inhibitor octanephosphonic (V1), do not compete, because these are the "fountain blacks" to reduce total assets.

The Use of non-tertiary amine compounds such as Aminomethylphosphonic acid (V3), however, results in Comparison with the inhibitor according to the invention B1, which is a tertiary amine compound worse results regarding the inhibition of "fountain blackness" especially for a short exposure time. The invention suppress chelating inhibitors B2-B4 again the unwanted discoloration of the workpiece almost completely up to an exposure time of 48 h and are the inhibitors used in the comparative examples Far superior to V1-V3.

All in all These experimental data clearly show the positive effect the chelating amine compounds of the invention (III b) on the suppression of irreversible blackening ("Fountain black") aluminum-containing magnesium materials.

The Increasing the filterability of the application solution (Oil-in-water emulsion) by adding alkoxylated Fatty amines (II c) to the emulsion concentrate is another aspect of the present invention experimentally demonstrated as follows.

In 1000 ml of a 5 wt .-% application solution of the emulsion concentrate according to Table 4, which was prepared with DIN 51360-water (20 ° dH), 15 g of aluminum alloy magnesium turnings (AZ91) for 24 h at a temperature of 40 ° C stirred. Thereafter, the chips are separated over a pleated filter. From the thus prepared emulsion, the passage time t _D of 100 ml of the application solution is determined by a cellulose nitrate filter with a pore size of 3 microns at atmospheric pressure.

The throughput time t _D as a measure of the filterability of the application solution is already significantly reduced by about 40% compared with a cocoamine (12 EO) -free application solution (BV2) even at a weight fraction of 1% by weight. The optimum filterability of the use solution is achieved with a cocoamine (12 EO) content for the test series of about 2% by weight (B6) listed in Table 4. For other alkoxylated fatty amines according to the invention and other compositions of the emulsion concentrate, deviating values result for the optimum content of alkoxylated fatty amines, the filterability showing qualitatively the same dependency.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• - DE 19956237 A [0005, 0006]

Claims (18)

Oil-containing, water-miscible emulsion concentrate containing (I) an oil component (II) an emulsifier system containing a) 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 b) 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 and (III) a corrosion protection system comprising a) straight-chain and / or branched carboxylic acids and / or phosphonic acids having 6 to 12 C atoms, characterized in that the corrosion protection system (III) additionally contains chelating organic amine compounds (III b) having one or more tertiary nitrogen atoms whose organic radicals contain functional groups selected from -OP (OO) (OX) ₂ , -P (OO) (OX ) ₂ , -PH (= O) OX, -COOX and / or represent an aliphatic group with not more than 4 C-atoms, wherein the organic radicals of Compounds (III b) having terminal tertiary-substituted nitrogen atoms or the organic radicals of compounds (III b) having only one tertiary-substituted nitrogen atom, at least two functional groups selected from -OP (= O) (OX) ₂ , -P (= O) ( OX) ₂ and / or -PH (= O) OX, and X is a hydrogen atom, an alkali metal cation, an ammonium ion, a quaternary ammonium compound and / or an aliphatic radical having not more than 4 C atoms. Oil-containing, water-miscible emulsion concentrate according to claim 1 containing i) 5 to 50% by weight the oil component (I), ii) 2 to 50% by weight of the emulsifier system (II) containing the components II a to II b, wherein the weight ratio of components a: b can vary from 1: 0.3 to 0.3: 1, iii) 2 to 15 wt .-% of the corrosion protection system (III), wherein the weight fraction the chelating organic amine compounds (III b) on the emulsion concentrate between 0.05 and 2 wt.%, and optionally other excipients and active ingredients (IV), where the sum of the constituents I) to IV) constitutes 60 to 95 wt .-% and the remaining weight fraction Represents water. Oil-containing, water-miscible emulsion concentrate according to one or both of the preceding claims, characterized in that the chelating organic amine compounds (III b) correspond to the general structural formula (A),

wherein the organic substituent Y contains at least one functional group selected from -OP (= O) (OX) ₂ , -P (= O) (OX) ₂ , -PH (= O) OX, -COOX and / or an aliphatic group with no more than 4 carbon atoms and the organic substituent Z contains at least one functional group selected from -OP (= O) (OX) ₂ , -P (= O) (OX) ₂ , -PH (= O) OX and in which the radicals R ¹ and R ² independently of one another and independently of the x constituent units (CR ¹ R ² ) are hydrogen atoms, aliphatic radicals having not more than 4 C atoms or substituents Y, x is at least 1 and at most 4 and n is at least 2. Oil-containing, water-miscible emulsion concentrate according to one or more of the preceding claims, characterized in that the functional groups -OP (= O) (OX) ₂ , -P (= O) (OX) ₂ , -PH (= O) OX, - COOX of the chelating organic amine compounds (III b) in each case and independently of one another in α, β or γ position to the tertiary nitrogen atom. Oil-containing, water-miscible emulsion concentrate according to one or more of the preceding claims 1 to 3, characterized in that as chelating organic amine compounds (III b) compounds corresponding to the general structural formula (B) are used:

wherein n is at least 1, but not greater than 8 and preferably 3, and the substituents X are independently selected from hydrogen atoms, alkali metal cations, ammonium ions, quaternary ammonium compounds or aliphatic radicals having not more than 4 carbon atoms, preferably from Hydrogen atoms and alkali metal cations. Oil-containing, water-miscible emulsion concentrate according to one or more of the claims 2 to 5, characterized in that the corrosion protection system (III) additionally contains non-ferrous metal inhibitors, preferably selected from the group of triazoles, in particular from Benzotriazoles and tolyltriazoles, preferably in an amount of 0.1 to 1 part by weight of the emulsion concentrate. Oil-containing, water-miscible emulsion concentrate according to one or more of the preceding claims, characterized in that as the oil component (I) paraffinic or naphthenic mineral oil, dialkyl ethers of 12 to 20 C atoms and / or ester oils are used. Oil-containing, water-miscible emulsion concentrate according to one or more of the preceding claims, characterized in that the emulsifier system (II) additionally alkoxylated fatty amines (II c) with a weight fraction of the emulsion concentrate of at least 1% by weight, preferably at least 2% by weight, but not more than 10% by weight, preferably not more than 8% by weight. Oil-containing, water-miscible emulsion concentrate according to claim 8, characterized in that as alkoxylated fatty amines (II c) of the emulsifier system (II) one or several saturated and / or unsaturated aliphatic Amines with 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 more preferably not more than 16 carbon atoms, which are at least 8, preferably at least 10, but not more than 16 and preferably not more than 14 and more preferably 12 Ethylene oxide units are ethoxylated used. Oil-containing, water-miscible emulsion concentrate according to one or more of claims 2 to 9, characterized in that the emulsifier system (II) additionally contains ether carboxylic acids (II d) or their anions of the general formula (B), RO- (CHA-CH ₂ -O) _n - (CH ₂ ) _m -COOH (B) where R is a saturated or unsaturated, linear or branched alkyl radical having 5 to 22 C atoms, A is hydrogen or a methyl group, n is a number in the range from 1 to 15 and m is a number in the range from 1 to 3, and wherein the weight ratio a: b: d of the constituents of the emulsifier system (II) except for the ethoxylated fatty amines (II c) is between 1: 0.3: 0.1 and 1: 4: 1. Oil-containing, water-miscible emulsion concentrate according to one or more of the claims 2 to 10, characterized in that as auxiliary and active ingredient (IV) additionally a buffer system based on boric acid / borate is contained, preferably in an amount based on the equivalent Amount of boric acid from 2 to 10 parts by weight of the emulsion concentrate. Oil-containing, water-miscible emulsion concentrate according to one or more of the claims 2 to 11, characterized in that as auxiliary and active ingredient (IV) additionally contain triethanolamine and / or glycerol are, preferably in an amount of 1 to 6 parts by weight on the emulsion concentrate. Oil-containing, water-miscible emulsion concentrate according to one or more of claims 2 to 12, characterized in that as auxiliary agents and active ingredients (IV) additionally lubricating additives, EP additives, Kon Serving and / or biocides are contained, preferably in an amount of 0.1 to 2 parts by weight of the emulsion concentrate. Oil-in-water emulsion, available by mixing from 0.5 to 10 parts by weight of an oil-containing, water-miscible Emulsion concentrate according to one or more of the claims 2 to 13 with 99.5 to 90 parts by weight of water. Oil-in-water emulsion according to claim 14, characterized in that the pH of the emulsion is not greater than 10, preferably not greater than 9.5 and is not less than 8, preferably not less than 8.5. Use of the emulsion according to claim 14 or 15 as cleaning, corrosion protection or cooling lubricant emulsion. Use of the emulsion according to claim 14 or 15 as cooling lubricant emulsion during machining of light metals, in particular of aluminum and its alloys and particularly preferably of aluminum-alloyed magnesium. Use of the emulsion according to claim 14 or 15 in conjunction with claim 6 as a cooling lubricant emulsion in the machining of non-ferrous metals.