EP1108073B1 - Agent and method for machining metal and for cleaning metal or anticorrosion treatment - Google Patents

Abstract

A process for metal cutting using a water-mixed cutting compound and subsequent cleansing and corrosion protective treatment wherein an oil in water emulsion is used as a cutting compound which contains;(I) an amount emulsifier system consisting of:(a) ethyoxylates/propoxylates of fatty alcohols having 8 to 18 carbon atoms in the alcohol, which contains 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units;(b) fatty alcohols and/or fatty alcohols propoxylates having 12 to 24 carbon atoms in the alcohol and 0 to 3 propylene oxide units and/or distillation residues of such fatty alcohols;In a ratio by weight, a:b=1:0.2 to 0.2:1;and(ii) corrosion inhibitory; and an aqueous solution or suspension is used for cleansing an anti-corrosion treatment which contains the same emulsifier system and the corrosion inhibitors as the cutting compound. The cutting compound and the cleansing and corrosion protective treatment material comprise a systems for treating the metal during cutting and cleansing.

Description

The invention is in the field of metalworking and relates to the Steps: metal cutting and subsequent cleaning and / or anti-corrosion treatment. Here are under "metal cutting machining" understood machining operations, at which the shape of a piece of metal is changed by using a Machining tool Material from the workpiece to be machined Will get removed. Examples of such cutting Metalworking processes are drilling, turning, milling and grinding. For such machining operations it is necessary to use tools and Rinse the workpiece with a liquid coolant. This one has the Tasks: lubricate the tool to weld and To avoid overheating, dissipation of the heat and Removal of the chips or other metal particles formed. It must the cooling lubricant should be such that it corrodes the Workpiece prevented.

In technology, oils, oil-in-water emulsions or are used as cooling lubricants water-soluble cooling lubricants that only consist of an aqueous solution, known. The present invention is concerned with oil-in-water emulsions and their water-miscible concentrates, i.e. cooling lubricants, the one Oil component included.

In the processing chain of a metallic workpiece, this is after a Machining usually cleaned and / or against corrosion protected. The cleaning should remove residues of the cooling lubricant, but also other dirt as well as adhering metal particles are removed become. So far, the nature of the before the cleaning step for metalworking coolant used only in so far as the cleaner must be able to remove it. The entire cooling lubricant represents a "dirt load" for the cleaner, which makes the cleaner unusable over time. Depending on the load with The cleaner must use cooling lubricant either with new active cleaning agents Components added, regenerated through bathroom care measures or discarded and re-scheduled. This leads to high consumption Detergent ingredients, each after the end of the cleaner life must be disposed of. This entails and is an environmental burden also economically disadvantageous because of the required use of materials.

The object of the invention is to provide a combination of means and methods metal cutting using a water mixed Cooling lubricant and subsequent cleaning and / or corrosion protection of the processed metal parts with an aqueous cleaning / corrosion protection agent to provide, in which the ingredients of the cooling lubricant and the aqueous cleaning / corrosion protection agents are so coordinated that the coolant contains the cleaning / corrosion protection agent complement or at least not negatively influence. According to this concept the cooling lubricant does not provide for the cleaning / corrosion protection agent "Dirt pollution", but rather complements it. This allows for that Cleaning / corrosion protection agents even a lower use Agents. The service life of the cleaning / corrosion protection agent is also extended without bathroom care measures. Reduced use of fabric and less Disposal efforts relieve the environment and make the entire process cheaper.

In a first aspect, the invention relates to a combination of agents according to claims 1 and 4, respectively.

The emulsifier system to be used according to the invention is from the German one Patent application DE-A-197 03 083 known. Compared to conventional ones Emulsifier systems have the advantage that they are soft to medium hard Water, i.e. in water with less than 12 ° and in particular with less than 8 ° dH tends to foam little.

The composition of the emulsifier system and the molecular structure of the emulsifiers used must therefore meet stringent requirements. Firstly, according to 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 b) unalkoxylated fatty alcohols with 12 to 24 carbon atoms, their distillation residue or their alkoxylation products with up to a maximum of 3 propylene oxide units on average. Furthermore, the approximate weight ratio is to be observed. Distillation residues of fatty alcohols with 12 to 24 carbon atoms are available from Henkel KGaA, Düsseldorf, under the name Pernil ^R RU.

Non-polar or polar oils can be used as the oil component in the first agent petrochemical or native origin. Furthermore are suitable synthetic oil components. Examples of usable oil components are paraffinic or naphthenic mineral oil, dialkyl ethers with 12 to 20 carbon atoms and esterotes. The ester oils can be of vegetable or animal origin be and as an ester of glycerol with 3 fatty acids (so-called Fatty acid triglycerides). An example of such an ester oil is rapeseed oil. Such Ester oils can also be obtained synthetically by using glycerol with selected fatty acids esterified or that you can use natural fats and oils other fatty acids transesterified.

The corrosion inhibitors according to the invention both in aqueous Cooling lubricant as well as in the aqueous cleaning / corrosion protection agent as well as used in their concentrates are preferably selected from alkanolamines and / or from branched or unbranched, saturated or unsaturated aliphatic mono- or dicarboxylic acids with 6 to 10 carbon atoms and / or from aromatic carboxylic acids with 7 to 10 carbon atoms, the Some or all of the carboxylic acids are present as salts. If here of alkanolamines and salts of carboxylic acids, so can on the one hand, this means that the alkanolamine salts of the carboxylic acids can be used directly. This is equivalent to a mixture of Alkanolamines and carboxylic acids that work together to form salts react. Furthermore, the alkanolamines as such, the carboxylic acids as alkali metal salts, preferably as potassium salts. Mixtures of are equivalent to alkali metal salts of carboxylic acids Carboxylic acids and alkali metal hydroxides. Depending on the pH in the ready-to-use water-mixed cooling lubricant or in the Alkanolamines become aqueous cleaning / corrosion protection agents and / or the carboxylic acids as an equilibrium mixture of the Neutral molecules and the cations in the case of the alkanolamines or the Anions are present in the case of carboxylic acids.

The first agent (the cooling lubricant or its concentrate) and the second agent (the cleaning / anti-corrosion agent or its Concentrate) contain the same corrosion inhibitors. However, this is not mandatory. It is only necessary to ensure that both that first means and the second means one or more of each contain the aforementioned corrosion inhibitors. It is preferable however, that the first agent is one or more corrosion inhibitors contains, which are also present in the second means. Are the two remedies in a ready-to-use form during ongoing operation Carrying cooling lubricant residues into the cleaning / corrosion protection agent in the latter automatically one over time Combination of a corrosion inhibitor, which is also the first agent is available.

The first can be used for metal cutting Agent, the water-mixed coolant, in principle on site be mixed together that the individual components in the desired concentrations in water or emulsified. Technically However, it is common to use water-miscible cooling lubricants in the form of a Bring concentrate in the trade, the individual active ingredients in the correct proportion, but in a concentrated form. For the This concentrate must be applied to the site with water Application concentration can be diluted.

In principle, the aqueous cleaning / corrosion protection agent can also be used Prepare so that the individual active ingredients in water in the dissolve or suspend required concentrations. Like that However, cooling lubricant is also preferably carried out here in such a way that Brings concentrates of the cleaning / corrosion protection agent to the market, which are diluted on site with water in the required ratio.

Accordingly, both the first can in the combination of agents according to the invention Agent as well as the second agent are present as a water-miscible concentrate. contains.

The first agent 10 to 40% by weight of the oil components, 10 up to 40% by weight of the emulsifier system and 20 to 40% by weight Corrosion inhibitors. The second agent contains 10 to 40% by weight Emulsifier system and 20 to 40 wt .-% corrosion inhibitors. Both means can optionally contain additional water and / or other active substances and auxiliary substances, the proportions are of course to be chosen so that the Sum of the components is 100% by weight.

For example, the first agent can contain further active ingredients and auxiliaries: General lubrication additives and in particular so-called "extreme pressure" additives (EP additives), other corrosion inhibitors such as boric acid or alkylphosphonic acids and additional alkanolamines and solubilizers such as for example glycols, glycerin or sodium cumene sulfonate. For the use Special non-ferrous metal corrosion inhibitors can also be used to process non-ferrous metals be used. Examples include benzotriazole, Tolyltriazole, thiazoles or salts of pyridine thiol N-oxide. Can continue Biocides are added which extend the life of the concentrate Mix ready to use with water prepared Extend cooling lubricant emulsion. However, if necessary, such biocides the ready-to-use water-mixed cooling lubricant emulsion directly be added.

The first agent can be made exclusively from the oil component, the Emulsifier system and the corrosion inhibitors exist. the preparation, however, it usually contains small amounts of water, for example in the range from about 2 to about 10% by weight. These can either be used Raw materials in the agent, for example if you consider corrosion inhibitors Carboxylic acids are used, which are neutralized with aqueous potassium hydroxide solution. additionally can optionally the above-mentioned further active ingredients and auxiliaries to be present. The second agent necessarily contains at least as a concentrate 20% by weight of water and / or further active ingredients and auxiliaries. In the simplest case it contains 20 to 20 in addition to the emulsifier system and the corrosion inhibitors 70% by weight of water and no other active ingredients.

The second agent can be in the form of both its concentrate and its ready-to-use water-diluted preparation form Contain builder substances, biocides and / or complexing agents. Examples of builder substances are alkali metal orthophosphates, polyphosphates, -silicates, -borates, -carbonates, -poly-acrylates and -gluconates. This Builders sometimes have complex properties and have a water softening effect. Instead of or in addition to this can stronger complexing agents such as 1-hydroxyethane-1,1-diphosphonic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid become. There are also ethylenediaminetetraacetates or nitrilotriacetates into consideration.

The invention further relates to the combination of agents in a ready-to-use form, the cooling lubricant (the first agent) and the aqueous cleaning / corrosion protection agent (the second agent) as a water-diluted emulsion, Suspension or solution. The form of application of the first agent is always an oil-in-water emulsion. These ready-to-use aqueous Preparations of the first and the second agent can be obtained in that the concentrates of the first and the second agent each in one Weight ratio between about 0.5: about 99.5 to about 10: about 90 with Water mixed.

Here, the emulsifier system to be used according to the invention leads to the technical advantage that the ready-to-use aqueous preparations of The first and the second means little in soft water Tend to foam. For diluting the concentrates on the Application concentration can therefore not only hard water, but also medium hard water (less than 12 ° dH) or even soft water (less than 8 ° dH) can be used. Even water with a hardness of less than 4 ° dH can be used, sometimes even demineralized water, without the Use of the agent foam problems occur. The invention A combination of agents can therefore also be used in the spray process in the temperature range between the freezing point and the boiling point of the ready-to-use Preparations are used. A minimum temperature for In contrast to conventional neutral cleaners, spray applications do not have to be respected. Of course, the invention Medium combination can also be used in hard water without disadvantages.

The second agent is preferably used as a cleaning solution as a so-called Neutral cleaner formulated. The usual pH of this so-called Ready to use neutral cleaner is in the range of about 6.5 to about 9.

i) ein Emulgatorsystem bestehend aus

a) Ethoxylaten/Propoxylaten von Fettalkoholen mit 8 bis 18 C-Atomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten und

b) Fettalkoholen und/oder Fettalkoholpropoxylaten mit 12 bis 24 C-Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder Destillationsrückstand dieser Fettalkohole

   im Gewichtsverhältnis a : b = 1 : 0,2 bis 0,2 : 1.
und

ii) Korrosionsinhibitoren

enthält,
und daß man zur Reinigung und/oder Korrosionsschutzbehandlung eine wäßrige Lösung und/oder Suspension einsetzt, die das gleiche Emulgatorsystem wie der Kühlschmierstoff enthält.In a further aspect, the invention relates to a method for metal cutting using a water-mixed cooling lubricant and subsequent cleaning and / or corrosion protection treatment, characterized in that an oil-in-water emulsion is used as the cooling lubricant, which

i) an emulsifier system consisting of

a) ethoxylates / propoxylates of fatty alcohols with 8 to 18 carbon atoms in alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and

b) fatty alcohols and / or fatty alcohol propoxylates with 12 to 24 carbon atoms in the alcohol and 0 to 3 propylene oxide units and / or distillation residue of these fatty alcohols

in the weight ratio a: b = 1: 0.2 to 0.2: 1.
and

ii) corrosion inhibitors

contains
and that for cleaning and / or anti-corrosion treatment, an aqueous solution and / or suspension is used which contains the same emulsifier system as the cooling lubricant.

For details on the composition of the coolant agent to be used and the agent used for cleaning and / or Corrosion protection treatment used, the above applies here executed.

In the process according to the invention, the cooling lubricant is used preferably an oil-in-water emulsion, which is obtainable by that a concentrate of the first agent as in claim 1, the possible composition is explained in more detail above, in Weight ratio between about 0.5: about 99.5 to about 10: about 90 with Water mixed.

For cleaning and / or anti-corrosion treatment, preferably an aqueous solution or suspension is available that a concentrate of the second agent, as in claim 1 and explained in more detail in the above description, in Weight ratio between about 0.5: about 99.5 to about 10: about 90 with Water mixed. As explained above, this can also be done in each case medium hard or even soft water can be used without the application of the process according to the invention foam problems occur.

When used as a cleaning solution, the second agent is placed in the Ready-to-use, water-diluted form so that the temperature is in the range of about 15 to about 80 ° C. The cleaning in in a diving system or in a spraying system. Since the Spray cleaning is particularly effective, this is preferred Method. This shows the advantage of the one to be used Emulsifier combination that also in the entire temperature range Using soft water will not cause foam problems.

The inventive method has the further advantage that residues of Cooling lubricant that is in the cleaning / corrosion protection agent over the machined workpieces are entered, at most with regard to the Oil components a load of the cleaning / corrosion protection agent represent. Since the emulsifier system in both the cooling lubricant and Cleaning / anti-corrosion agent is the same and the cooling lubricant contains at least corrosion inhibitors that with those in the cleaning / corrosion protection agent are compatible, or preferably Contains corrosion inhibitors that are also in the cleaning / anti-corrosion agent there is a carryover of Coolant does not contaminate the cleaning / corrosion protection agent, but rather complements it. This will on the one hand prolongs the life of this product and on the other hand it is less often necessary to replenish these active ingredients. So that leads Process sequence according to the invention to a significantly reduced Use of materials and lower disposal costs. The technical Purpose of metal cutting with subsequent Cleaning and / or anti-corrosion treatment is done with an im Compared to the prior art, less material and with a lower environmental impact when disposing of the funds used reached. In addition, you avoid foam problems in case of carryover from the metal processing to the cleaning zone.

embodiments

The tables below contain examples of concentrates for the first and second agents of the agent combination according to the invention. In the corrosion protection test described below, it is shown that dragging coolant into the cleaning / corrosion protection agent does not worsen its corrosion protection effect, but rather improves it. Example 1 for a concentrate of a cooling lubricant emulsion (first agent), concentration data in% by weight Naphthenic white oil 30.0 3,5,5-trimethylhexanoic acid (= isononanoic acid) 17.5 caprylic 7.5 C12 / C14 fatty alcohol x 3 moles of ethylene oxide and 6 moles of propylene oxide 8.0 Oleyl / cetyl alcohol x 2 moles of propylene oxide 8.0 Fatty alcohol distillation residue 10.6 Monoethanolamine 7.9 potassium hydroxide 4,725 water 5,775 Example 2 for a concentrate of a cooling lubricant emulsion (first agent), concentration data in% by weight Paraffinic mineral oil 16.6 Rape 7.3 3,5,5-trimethylhexanoic acid (= isononanoic acid) 9.6 caprylic 9.6 C12 / C14 fatty alcohol x 3 moles of ethylene oxide and 6 moles of propylene oxide 8.5 Oleyl / cetyl alcohol x 2 moles of propylene oxide 8.5 Fatty alcohol distillation residue 16.0 triethanolamine 5.2 potassium hydroxide 7,425 Octanphosphaonsäure 0.45 Benzotriazole, 1H, 2,3- 0.2 Pyridinethiol-N-oxide Na 0.08 Benzylhemiformal 2.9 water 7,645 Example of a concentrate of a cleaning solution (second agent), concentration data in% by weight water 30.0 isononanoic 17.5 caprylic 7.5 Oleyl / cetyl alcohol x 2 moles of propylene oxide 8.0 C12 / C14 fatty alcohol x 3 moles of ethylene oxide and 6 moles of propylene oxide 8.0 Fatty alcohol distillation residue 10.6 Monoethanolamine 7.9 Potash lye 45% 10.5

From the concentrate of the second agent according to Table 3 ready-to-use cleaning / corrosion protection solutions are produced and hereby a corrosion protection test according to DIN 51360/2 was carried out. For this be Cast iron chips on a round filter wetted with the solution and for 2 hours kept in a glass bowl at room temperature. Then the Corrosion badges visually assessed on the filter paper and into the Corrosion levels 0 to 4 classified. Degree of corrosion means 0: none Corrosion, degree of corrosion 1: traces of corrosion, degree of corrosion 2: slight Corrosion, degree of corrosion 3: moderate corrosion and degree of corrosion 4: severe Corrosion.

With a 2% batch of the concentrate in industrial water (pH 9.72) there was a degree of corrosion 4 with a 3% mixture (pH 9.75) Degree of corrosion 0 and also with a 4% mixture (pH 9.78) Degree of corrosion of 0.

The cooling lubricant is carried over into the cleaning / corrosion protection solution was simulated by the above described ready-to-use solutions additionally with 0.2 wt .-% of Concentrate according to Table 2 were added. Then was on again Corrosion protection test carried out in accordance with DIN 51360/2. Results: 2% Batch (pH 9.66): degree of corrosion 2, 3% batch (pH 9.72): degree of corrosion 0, 4% mixture (pH 9.75): degree of corrosion 0.

A dragging of the cooling lubricant into the cleaner / corrosion protection solution deteriorates the degree of corrosion with 3 and 4% of the Cleaner concentrate not, with a 2% mixture the corrosion protection significantly improved.

Claims (7)

1. A combination of a first preparation for machining metals and a second preparation for subsequent cleaning and/or anti-corrosion treatment, characterized in that the first and the second preparation contain

   i) an emulsifier system consisting of

   a) ethoxylates/propoxylates of C_8-18 fatty alcohols containing 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and

   b) C_12-24 fatty alcohols and/or fatty alcohol propoxylates containing 0 to 3 propylene oxide units and/or distillation residues of these fatty alcohols,
   in a ratio by weight of a) to b) of 1:0.2 to 0.2:1

   and

   ii) corrosion inhibitors,

   the first preparation additionally containing an oil component and the first and the second preparation being present as water-miscible concentrates,
   the first preparation containing
   10 to 40% by weight of oil component,
   10 to 40% by weight of emulsifier system,
   20 to 40% by weight corrosion inhibitors
   and the second preparation containing
   10 to 40% by weight emulsifier system,
   20 to 40% by weight corrosion inhibitors
   and optionally water and/or other active ingredients and auxiliaries, the sum total of the components being 100% by weight.
2. A combination as claimed in claim 1, characterized in that the oil component in the first preparation is selected from paraffinic and naphthenic mineral oils, from C_12-20 dialkyl ethers and from ester oils.
3. A combination as claimed in one or both of claims 1 and 2, characterized in that the corrosion inhibitors are selected from alkanolamines and/or from branched or unbranched, saturated or unsaturated aliphatic C_6-10 mono- or dicarboxylic acids and/or aromatic C_7-10 carboxylic acids, the carboxylic acids being partly or completely present as salts.
4. A combination of a first preparation for machining metals and a second preparation for subsequent cleaning and/or anti-corrosion treatment, characterized in that the first and the second preparation contain

   i) an emulsifier system consisting of

   a) ethoxylates/propoxylates of C_8-18 fatty alcohols containing 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and

   b) C_12-24 fatty alcohols and/or fatty alcohol propoxylates containing 0 to 3 propylene oxide units and/or distillation residues of these fatty alcohols,
   in a ratio by weight of a) to b) of 1:0.2 to 0.2:1

   and

   ii) corrosion inhibitors,

   the first preparation additionally containing an oil component, characterized in that the first preparation and the second preparation are present as water-diluted emulsions, suspensions or solutions obtainable by mixing concentrates of the first and second preparations according to one or more of claims 1 to 3 with water in a ratio by weight of 0.5:99.5 to 10:90.
5. A process for machining metals using a water-mixed cooling lubricant and subsequent cleaning and/or anti-corrosion treatment, characterized in that the cooling lubricant used is an oil-in-water emulsion containing

   i) an emulsifier system consisting of

   a) ethoxylates/propoxylates of C_8-18 fatty alcohols containing 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and

   b) C_12-24 fatty alcohols and/or fatty alcohol propoxylates containing 0 to 3 propylene oxide units and/or distillation residues of these fatty alcohols,
   in a ratio by weight of a) to b) of 1:0.2 to 0.2:1

   and

   ii) corrosion inhibitors,

   and in that cleaning and/or the anti-corrosion treatment is/are carried out using an aqueous solution and/or suspension containing the same emulsifier system and the same corrosion inhibitors as the cooling lubricant.
6. A process as claimed in claim 5, characterized in that an oil-in-water emulsion obtainable by mixing a concentrate of the first preparation according to one or more of claims 1 to 3 with water in a ratio by weight of 0.5:99.5 to 10:90 is used as the cooling lubricant.
7. A process as claimed in claim 5, characterized in that an aqueous solution or suspension obtainable by mixing a concentrate of the second preparation according to one or more of claims 1 to 3 with water in a ratio by weight of 0.5:99.5 to 10:90, is used for cleaning and/or for the anti-corrosion treatment.