EP2705128B1 - Fluide de travail de métal - Google Patents

Fluide de travail de métal Download PDF

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Publication number
EP2705128B1
EP2705128B1 EP12719676.4A EP12719676A EP2705128B1 EP 2705128 B1 EP2705128 B1 EP 2705128B1 EP 12719676 A EP12719676 A EP 12719676A EP 2705128 B1 EP2705128 B1 EP 2705128B1
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Prior art keywords
weight
ethoxylated
acid
composition
compounds
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EP12719676.4A
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German (de)
English (en)
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EP2705128A1 (fr
Inventor
Yixing ZHAO
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Chemetall GmbH
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Chemetall GmbH
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/24—Emulsion properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to the field of water-based metalworking compositions.
  • the invention relates especially to aqueous, environmentally friendly, recyclable, synthetic, amine-free, petroleum oil-free and VOC-free metalworking compositions which are to a high extent free of hazardous materials and which are compatible with a wide range of metal alloys.
  • Metalworking compositions are employed in many metal treatment operations such as cutting, grinding, forming, lapping, drawing, forming, pressing, punching, rolling, stamping and others to lubricate and to cool the metalworking tool, to flush off the metallic chips and impurities if there should be some from the workpiece and to protect the tool and parts of a machine from damage, wear and corrosion as far as possible.
  • Such treatments comprise cutting operations showing a metal removal like grinding, turning, milling, tapping, broaching and hobbing as well as forming operations showing mostly no metal removal like bending, hot and cold rolling, drawing, forging, stamping and blanking.
  • the metalworking compositions may assist to flush away oil and debris from these metallic components. And they shall provide to these components corrosion protection.
  • the main classes of metalworking compositions are the straight oil type and the water-based type.
  • the water-based types may be further differentiated into the following types:
  • metalworking compositions are petroleum oil-based dispersions or emulsions of water and oil.
  • a content of petroleum oil in any metalworking composition causes several problems like the following: 1.) poor heat conductivity so that there is a lower cooling effect, 2.) it enables microbial growth and may harm workers, 3.) petroleum oil causes misting and residues that are difficult to be cleaned off, 4.) disposal problems and not environmentally friendly and 5.) water hardness may impact the emulsion stability. Therefore, there is the need to further develop petroleum oil-free metalworking compositions. Therefore, industry is turning toward the use of water-based metalworking compositions.
  • Alkanolamines have the disadvantages that some of these are very hazardous compounds and environmentally unfriendly, that some of these cause a high volatile organic content VOC and that some of these cause irritations and illness of the skin and body. Further on, these compounds may lead to strong smelling.
  • a metalworking composition should be capable of sequestering and removing debris, contaminants and oils from the metallic components and should provide good corrosion protection to all metallic components. But further on, such compositions are often micro-emulsions or macro-emulsions, which need to be stable not to split the emulsion as far as possible, at the same time as a concentrate and as a dilution which has been gained by diluting the concentrate with a low or a high amount of water. The more severe a metalworking operation is, the higher should be the concentration of the metalworking composition applied. For metalworking operations of low requirements like a grinding, a dilution to 5 % by weight of the metalworking composition may be sufficient.
  • a dilution to 10 to 15 % by weight of the metalworking composition should be used. Further on, these compositions need to be non-foaming or low foaming compositions, when used for any metalworking operation. And these compositions should be more and more environmentally friendly.
  • several amine-containing metalworking compositions were used, as the amines and especially the alkanolamines help in bio-resistance, corrosion protection and emulsion stability, but several amines are very toxic and participate in volatile organic compounds VOC too.
  • the formulation of aqueous metalworking compositions without using any amine is much more difficult. For universal application of one metalworking composition, the coverage of the whole range of properties and chances is expected.
  • the present invention is directed to an aqueous metalworking composition which provides very good lubricity without the aid of any petroleum oil for all kinds of metallic materials and very good stability.
  • the metalworking compositions of the present invention are therefore compatible with, and non-corrosive toward, a wide variety of metals and alloys. They remove petroleum oils, dirt and debris well from the metallic components. They are environmentally friendly, low foaming, corrosion protecting, recyclable, long time usable and may be resistant to biological growth.
  • compositions may be used for cold forming operations, wherein cold forming includes: slide drawing (forming under a combination of tensile and compressive conditions), e.g. of welded or seamless tubes, hollow profiles, rods, solid profiles or wires, ironing and/or deep drawing, e.g. of strips, sheets or hollow parts to form hollow parts, cold extrusion (forming under compressive conditions), e.g. of hollow or solid parts and/or cold heading, e.g. of wire sections to form joining elements such as e.g. nut or screw blanks.
  • slide drawing forming under a combination of tensile and compressive conditions
  • hollow profiles e.g. of welded or seamless tubes
  • hollow profiles e.g. of rods, solid profiles or wires
  • ironing and/or deep drawing e.g. of strips, sheets or hollow parts to form hollow parts
  • cold extrusion forming under compressive conditions
  • cold extrusion e.g. of hollow or solid parts and/or cold heading, e.g.
  • US 7,018,959 B2 discloses a water-based, recyclable metalworking fluid which comprises an aqueous solution of a polyalkylene glycol, an alkanolamine, a polyglycol surfactant, a polyol surfactant, a biocide package and a corrosion inhibitor.
  • US 2009/0149359 A1 concerns compositions and constituents for aqueous metalworking compositions, but any details are only described to a certain extent in the examples.
  • the pH of these compositions shall be at least 3, but acidic pH values are only acceptable for aluminum based metallic materials and not for steels.
  • the use of aqueous metalworking compositions for steels is much more complicated than for aluminum based metallic materials and often requires high pH values.
  • the best properties gained are disclosed for sample C, which will be compared in this application in Table 4 too. This publication indicates the use of amines and even of alkanolamines as well as of many other compounds.
  • An object of the present application is to propose an environmentally friendly metalworking composition which shows high lubricity, a high stability and a good corrosion protection.
  • Another object of the present application is to propose a composition that is well usable for multi-metal metalworking operations. Further on, there is an object to propose a method to prepare a stable metalworking emulsion.
  • the aqueous metalworking composition of the present invention is an aqueous metalworking composition according to claim 1.
  • the present invention relates further to a method to prepare an aqueous metalworking composition by first adding to water any compounds (b) and (d), then adding any compounds (a) and afterwards then (c), during which mixing procedure until here a heating to temperatures in the range of from 30 to 50 °C and an agitation is used, and optionally then all other compounds are added.
  • the present invention relates further to a method of use of an aqueous metalworking composition of the present invention as a coolant, as a lubricant and/or for bending, for blanking, for boring, for broaching, for cooling, for cutting, for drawing, for drilling, for forging, for grinding, for hobbing, for honing, for hydroforming, for lapping, for lubricating, for forming, for milling, for pressing, for punching, for reaming, for cold rolling, for hot rolling, for sawing, for stamping, for tapping, for threading, for turning or for any combination thereof.
  • the present invention relates finally to a metalworking process characterized in that the metalworking operation is performed by flushing, spraying, high pressure spraying, brushing, flowing, fluting, roll coating, immersion or any combination thereof with the aqueous metalworking composition of the invention.
  • the aqueous metalworking composition of the invention is of low VOC, which typically means a content of volatile organic compounds of less than 1 % by weight. More preferred, the aqueous metalworking composition of the invention is of zero-VOC or is preferably petroleum oil-free or is preferably alkanolamine-free or is amine-free or is preferably free of any combination thereof, at least until start of its application in a metalworking operation.
  • VOC means "volatile organic compounds” and comprises in praxis petroleum oil and specifically low-molecular weight petroleum oil, organic solvents and alkanolamines.
  • the metalworking composition is in many embodiments even amine-free or there is not added any amine intentionally during formulation and preparation of the metalworking composition, at least until start of its application in a metalworking operation.
  • the metalworking composition of the present application may comprise an alkanolamine or an alkyl amine or an oil content or any combination thereof in a total content in the range of from 0.01 to less than 5 % by weight or in such a content that the test method of Environmental Protection Agent of US government EPA24 does not allow to detect a content of VOC.
  • the aqueous metalworking composition is free from any ammonium content and of ammonia, at least until start of its application.
  • the compositions are substantially free or totally free of organic solvents, of strongly acidic compounds, of waxes, of chlorinated fatty acids and their esters with chain lengths ⁇ C12 and/or of heavy metals like chromium and nickel.
  • the composition has a pH in the range of from 5 to 14, more preferred of from 7 to 13.5 or of from 8 to 13 or of 9 to 12 or of 10 to 11 in general, for a concentrate as well as for a diluted composition.
  • a pH > 13 no technical problem occurs with a metalworking composition.
  • Most compositions are therefore slightly or strongly alkaline.
  • the alkalinity may be necessary for corrosion protection, for emulsification and emulsion stability and for bio-stability.
  • the pH value respectively the degree of alkalinity does often not influence the stability or lubricity of the aqueous metalworking composition. If there is a low pH, this may result in corrosion and rusts on the parts and on machines and in the growth of bacteria.
  • the alkalinity of the composition is mostly caused by the addition of at least one compound of an alkalinity agent (d).
  • a low alkalinity corresponds to a low pH.
  • the composition may have a good lubricity especially on aluminum based metallic parts, but a very bad corrosion protection. Any pH value significantly lower than optimum may increase the danger of phase separation in a metalworking emulsion, and therefore of inconsistent lubricating action.
  • the composition may have a good corrosion protection and a good lubricity on metallic materials that do not show alkaline attack, but aluminum, zinc and their alloys may be dissolved at a pH greater than 12. The best results are often gained with a pH in the range of from 7 to 10.
  • the chemical compounds may be applied in the aqueous metalworking composition independently one to the other in ionic, unstable or stable, hypothetical, unreacted and/or any reacted form of any other chemical species defined by number and type of atoms present, as well as in compounds with well defined molecules.
  • the present invention relates to an aqueous metalworking composition
  • an aqueous metalworking composition comprising in a concentrate or after dilution of a concentrate with water in a diluent at least one compound of each class of compounds from the components (a), (b), (c), (d) and (e):
  • a first necessary ingredient of the composition according to this invention is its primary lubricity imparting component (a), which contains the primarily lubricity imparting compounds.
  • the compounds (a) are water-insoluble. Usually, the compounds (a) spend additionally good corrosion resistance and good emulsification.
  • a vegetable oil respectively an animal oil contains a mixture of quite different carboxylic acids and their derivatives.
  • Such oil(s) may be independently one to the other be purified, refined, conditioned, chemically modified, synthesized or prepared by any combination thereof.
  • there is added to the metalworking composition at least one specific compound (a) or at least one chemical product having a compound (a) as main compound and optionally any other compound (a).
  • the metalworking composition comprises at least two or at least three or at least four different specific compounds (a). This enables chances for synergistic property effects.
  • Component (a) is contained in a range of from 6 to 40 % by weight.
  • component (a) is contained in a range of from 6 to 36 % by weight or of from 6 to 32 % by weight or of from 6 to 28 % by weight or of from 6 to 24 % by weight or of from 6 to 20 % by weight or of from 6 to 17 % by weight or of from 6 to 14 % by weight or of from 6 to 12 % by weight or of from 6 to 10 % by weight or of from 6 to 8 % by weight, independently if it is a concentrate or a dilution. If there would be a lower content of component (a), the metalworking composition would not be effective, but if it would have a higher content, it would often not be a stable composition.
  • the compounds of component (a) are selected from the group of compounds consisting of compounds (a1), (a2) and/or (a3).
  • Compounds (a1), (a2) and/or (a3) may optionally be assisted by an addition of an optional compound A.
  • the metalworking composition contains at least one compound (a1) as defined in claim 1.
  • Compounds (a1) are fatty acids and are selected from the group consisting of lauric/dodecanoic acid, myristic/tetradecanoic/myristoleic acid, pentadecanoic acid, palmitic/hexadecanoic/palmitoleic/hexadecapolyenoic acid, margaric/margaroleic acid, ricinoleic acid, stearic/octadecanoic acid, linoleic/eicosanoic acid, oleic acid, linoleic/linolenic/octadecatetraenoic acid, arachidic/gadoleic/eicosadienoic/arachidonic/eicosapentaenoic acid, heneicosanoic acid, behenic/docosanoic/erucic/docosapolyenoic acid, docosahexaenoic acid and lignoce
  • a more preferred base spend e.g. oleic acid or similar compounds (a1) as contained with an essential content e.g. in rapeseed oil, castor oil, coconut oil, soybean oil, sunflower oil, lard oil or any combination thereof. If the number of carbon atoms of such oil or compound would be lower than 12 per chain, it may occur that these compounds are not effectively in lubricity, but if the number of carbon atoms would be higher than 24 per chain, it may occur that the metalworking composition is no stable composition.
  • oleic acid has 18 carbon atoms.
  • castor oil contains in about 85 to 95 % by weight of ricinoleic acid, which has 18 carbon atoms too. Since castor oil exists as a triglyceride, which ester may be based on one glycerol unit with three ricinoleic acid units, the total number of carbon atoms in castor oil is often of about 57.
  • Another common vegetable oil which may be used as lubricity additive is rapeseed oil. Often in about 41 % by weight of rapeseed oil is erucic acid. The total number of carbon atoms of the triglyceride of erucic acid is 69.
  • the aqueous metalworking composition of the invention comprises preferably at least one triglyceride (a2) as defined in claim 1.
  • Especially preferred derivatives (a3) of (a2) are esters.
  • the triglycerides show side-chains that are identical or different independently one to the other and the fatty acids of the triglycerides have independently one to the other a "medium chain length” or a "long chain length". Such chains are called to be of “medium chain length” or of "long chain length” if they contain 6 to 12 carbon atoms respectively 14 to 24 carbon atoms independently one to the other.
  • a triglyceride is an ester derived from glycerol and three fatty acids. It is the main constituent of vegetable oil and animal fats.
  • a specific example of an unsaturated fat triglyceride is based on glycerol and on the other side of palmitic acid, oleic acid and alpha-linolenic acid, C 55 H 98 O 6 .
  • Triglycerides are triesters of glycerin.
  • the water-insoluble triglycerides (a2) as defined in claim 1 are triglycerides of three identical or two or three different carboxylic acids and especially triesters based on oleic acid, stearic acid, ricinoleic acid, erucic acid, lignoceric acid and/or lauric acid.
  • the metalworking composition contains at least one compound (a3) as defined in claim 1, which is a derivative of compound (a1) or (a2) or both and has independently one to the other 12 to 5.000 carbon atoms.
  • Preferred derivatives (a3) are chlorinated or sulfurized derivatives - which may optionally be used as extreme pressure additives too -, esters, ethers, ethoxylates, ethoxylate-propoxylates, propoxylates, alkali metal salts, alkaline earth metal salts and/or compounds having been condensed with at least one carbocylic acid like ricinoleic acid. More preferred derivatives are esters, ethoxylates, ethoxylate-propoxylates and/or propoxylates. Preferably, the derivatives have of from 14 to 170 or of from 16 to 130 or of from 18 to 100 or of from 20 to 70 or of from 22 to 52 or of from 24 to 42 carbon atoms.
  • ricinoleic acid ester and polymerized ricinoleic acid ester, which last one may be a condensation product of about four molecules.
  • triglycerides ethoxylated castor oil, castor oil each having 12 to 120 carbon atoms, may be used.
  • the lubricity imparting compound(s) (a) has/have a water-solubility at 20 °C of less than 0.05 g/liter or of less than 0.001 g/liter.
  • concentration of the cation is not further specified.
  • these cations are selected from alkali metals and alkaline earth metals. As cations, sodium and potassium are most preferred, but others may be used too.
  • the degree of neutralization or of ionization of the acid or of the salt may change in the process of preparation, dilution or application in the actual metalworking composition. All these different conditions are included within the general measures of the invention.
  • the metalworking composition contains 0.002 to 30 % by weight of component (b) comprising at least one water-soluble corrosion inhibiting compound (b) which has a water-solubility at 20 °C of more than 0.1 g/liter. More preferred, the water-soluble corrosion inhibiting compound(s) (b) has/have a water-solubility at 20 °C of more than 0.5 g/liter or of more than 1 g/liter or of more than 5 g/liter.
  • the water-soluble compounds (b) contribute to the bio-stability of the aqueous metalworking compositions.
  • the water-soluble compounds (b1) and (b3) to (b5) may aid in the metalworking composition to improve stability of the emulsion.
  • component (b) or the at least one compound (b) is contained in a range of from 0.1 to 36 % by weight or of from 0.3 to 32 % by weight or of from 0.7 to 28 % by weight or of from 1 to 24 % by weight or of from 1.5 to 20 % by weight or of from 2 to 17 % by weight or of from 3 to 14 % by weight or of from 4 to 12 % by weight or of from 5 to 10 % by weight or of from 6 to 8 % by weight, independently if it is a concentrate or a dilution.
  • the content of the metalworking composition of the at least one corrosion inhibiting compound (b) would be lower, it may occur that the component (b) is not effective, but if it would have a higher content, it may occur that the metalworking composition is no stable composition.
  • the corrosion inhibiting component (b) contains at least two or at least three or at least four different compounds (b), especially to optimize corrosion protection.
  • mixture of corrosion inhibiting compounds may enhance the corrosion protection effect strongly without adding a too high amount of such compounds. Such mixtures enable chances for synergistic property effects.
  • the metalworking composition contains at least one corrosion inhibiting compound (b) which is selected from the group consisting of more or less well water-soluble compounds (b1).
  • the metalworking composition contains at least one compound (b1), which is a straight and/or branched, a saturated and/or unsaturated water-soluble compound and which has in total 6 to 40 carbon atoms and having chain lengths of 4 to 12 carbon atoms. More preferred, the compounds (b1) have independently one to the other 6 to 10 or 6 to 8 carbon atoms per aliphatic chain.
  • the compounds (b1) are selected from the group of compounds consisting of monocarboxylic acids, dicarboxylic acids, tricarboxylic acids and polycarboxylic acids and their alkali metal salts and alkaline earth metal salts. Preferably, there are monocarboxylic acids, dicarboxylic acids and/or their derivatives used. For example, the water solubility of C8-monocarboxylic acid (caprylic acid) in water at 20 °C is 0.7 g/liter.
  • the following compounds (b2)-(b5) may optionally be present in the composition but are not counted as (b) compounds with respect to the type and amount of (b) required by claim 1.
  • Preferred compounds (b2) are boric acid, its salts like its alkali metal salts and its alkaline earth metal salts and boric acid esters.
  • a boric compound (b2) may in addition assist in bio-stability.
  • Preferred compounds (b3) are imidazoles, imidazolines and their derivatives like their esters and salts, especially like their alkali metal salts and alkaline earth metal salts, for example benzimidazoles and their salts.
  • the preferred thiazoles and their derivatives (b4) comprise especially their alkali metal salts, alkaline earth metal salts and esters, for example benzothiazoles, mercaptobenzothiazoles and their salts and esters.
  • the preferred triazoles and their derivatives (b5) comprise especially their salts and esters and as examples benzotriazoles, tolyltriazole C 7 H 7 N 3 , and their derivatives as well as alkali metal salts, alkaline earth metal salts and esters of triazoles.
  • compositions according to this invention are a component (c) containing at least one emulsifying and/or dispersing compound (c) as defined in claim 1.
  • the metalworking composition contains 0.002 to 45 % by weight of at least one emulsifying and dispersing agent (c) which contains at least one emulsifying and/or dispersing compound (c) which is water-soluble, water-miscible or water-dispersable and which is selected from the group consisting of non-ionic, anionic and zwitterionic surfactants and which may be in some instances even corrosion inhibiting.
  • the compounds (a) and (b) often are hydrophobic, the composition would separate into droplets or even bigger drops or layers or any combination thereof, if no emulsifying and dispersing agent is added.
  • the metalworking composition would not be effective, but if it would have a higher content, then it would often not be a stable composition.
  • the emulsifying agent and dispersing agent (c) is contained in the metalworking composition of the invention in a range of from 0.01 to 40 % by weight or of from 0.05 to 35 % by weight or of from 0.1 to 32 % by weight or of from 0.5 to 25 % by weight or of from 1 to 20 % by weight or of from 3 to 15 % by weight or of from 5 to 12 % by weight, independently if it is a concentrate or a dilution.
  • the emulsifying agent and dispersing agent (c) has a HLB in the range of from 1 to 40 or of from 6 to 24 or of from 8 to 16 or of from 10 to 12.
  • the emulsifying agent and dispersing agent (c) is selected from surfactants that all have a HLB value in the range of from 1 to 40 or of from 6 to 24 or of from 8 to 16 or of from 10 to 12.
  • the individual emulsifying and/or dispersing compounds (c) have a HLB value in the range of from 1 to 40 or of from 6 to 24 or of from 8 to 16 or of from 10 to 12.
  • the emulsifying and dispersing agent (c) contains at least two or at least three or at least four different compounds (c), especially to gain a broad distribution of HLB within one composition.
  • Such combination of different compounds (c) offers chances to synergistic effects.
  • the emulsion may easily split into two or more layers one above the other. If the aqueous metalworking composition has an inadequate emulsifying effect because of wrong HLB range e.g. despite of adding a high amount of compound(s) (c), the emulsion may easily split into two or more layers one above the other. If the aqueous metalworking composition has a too high emulsifying effect, the emulsion may have a significantly lowered lubricity, may be high foaming and may have an insufficient corrosion protection effect.
  • the at least one emulsifying and/or dispersing compound (c) is selected from the group of non-ionic, anionic and zwitterionic surfactants consisting of:
  • these surfactants are selected one to the other independently to be ethoxylated or ethoxylated-propoxylated and without or with end-group capping.
  • the at least one emulsifying and/or dispersing compound (c) is selected from the group of non-ionic, anionic and zwitterionic surfactants consisting of:
  • the emulsifying compound or dispersing compound or both (c) is selected from non-ionic surfactants having 1 to 20 units of the sum of EO groups or from non-ionic surfactants having 2 to 40 units of the sum of EO and PO groups.
  • the at least one emulsifying and/or dispersing compound (c) shall aid in dispersing a second phase in an aqueous phase, in distributing solid particles, in stabilizing the dispersions and shall aid - if needed - in forming an emulsion.
  • the term dispersion shall include here emulsions and solutions. Most preferred, such compound (c) is used as emulsifier or dispersant or both. Therefore, it may in many embodiments helpful to add at least two or at least three different surfactants, of which the first one acts primarily as an emulsifier and at least one other primarily as dispersant respectively as a defoamer. This enables chances for synergistic property effects.
  • the alkalinity agent contributes to a higher stability of the emulsion and in the corrosion resistance and often in the bio-stability too.
  • the alkalinity assists that e.g. anionic surfactants may become be more stable.
  • the metalworking composition would not be sufficient alkaline, then the emulsion would not be stable enough, so that lubricity will be lowered or even go lost, the corrosion resistance may then be low too and microbial resistance will be lowered too. and that a metalworking composition gains a better corrosion protection and it may occur that an emulsifying agent does not work. If the alkalinity would be too high, the human skin of a worker may become irritated. It is in some embodiments preferred that the aqueous metalworking composition shall not have a pH higher than 12, but the concentrate may be much more alkaline. In some embodiments, a pH of about 14 does not disturb.
  • the metalworking composition contains 0.002 to 30 % by weight of an alkalinity agent (d) comprising at least one alkaline water-soluble compound (d1) selected from the group consisting of hydroxides and carbonates.
  • an alkalinity agent (d) comprising at least one alkaline water-soluble compound (d1) selected from the group consisting of hydroxides and carbonates.
  • an alkanolamine or of an alkyl amine or of both which may be selected from the group consisting of primary alkanolamines like amino-methyl propanol AMP, diglycolamine DGA, methanolamine MEA and monoisopropylamine MIPA, of secondary alkanolamines like diethanolamine DEA und diisopropanolamine DIPA and N-butylethanol amine nBEA, of tertiary alkanolamines like triethanol amine TEA and n-butyldiethanolamine nBDEA and of alkyl amines having an alkyl chain of 1
  • Such content of an alkanolamine or of an alkyl amine or of both is preferably in the range of from 0.01 to less than 5 % by weight or of from 0.1 to less than 2 % by weight or of from 0.2 to 0.8 % by weight.
  • the alkalinity agent (d) is contained in a range of from 0.01 to 25 % by weight or of from 0.1 to 20 % by weight or of from 1 to 15 % by weight or of from 3 to 12 % by weight.
  • the corrosion protection may be insufficient, but if higher content, the lubricity may be too low and the alkaline sensitive metallic materials may be chemically attacked and dissolved.
  • the at least one alkalinity compound (d) is added in an amount as to reach a predetermined pH value.
  • the alkalinity agent (d) is selected from hydroxides and carbonates of alkali metals and of alkaline earth metals (d1), for example potassium hydroxide, sodium hydroxide, a potassium carbonate, a sodium carbonate or any mixture of these.
  • Sodium and potassium compounds are the most preferred alkalinity agents. It will be apparent to those skilled in the art that many other alkalinity agents could be used in alternative thereto. But amounts for example of alkanolamines and/or often of all kinds of amines may lead to high VOC, to the irritation of human skin coming in contact with such composition and may generate strong smelling. Therefore the alkanolamines and/or often of all kinds of amines are therefore undesirable.
  • a transport component (e) has to be added to the mixture, which contains at least water. At least 0.004 % or at least 0.01 % by weight of a transport component (e) contains at least 98 % by weight of water. Primarily, predominantly, nearly totally or only water is the liquid compound contained in the metal working composition as the transport component (e) or as water.
  • a metalworking composition has a content of much more than 5 and until about 60 % by weight of a petroleum oil.
  • a petroleum oil-free metalworking composition which composition may be only polluted with any petroleum oil by its use in any metalworking operation, is especially preferred. In such a situation, the metalworking composition would be often only petroleum oil-free until a first application. If there is no content of a petroleum oil, the composition is in many embodiments of zero VOC; typically in most conventional metalworking compositions, they have a content of any of the compounds based on alkanolamines such as triethanolamine, on organic solvents, on petroleum oils and on low molecular weight petroleum oils, all causing a medium or often high value of volatile organic compounds VOC.
  • the transport component (e) may comprise in seldom embodiments even a small content of an organic solvent like an alcohol.
  • the aqueous metalworking composition may then contain seldom more than 1 % by weight of an alcohol. But mostly, such solvents are not added intentionally, but may be contained in raw materials or are impurities in the process. It has been found that if any amounts of petroleum oil or of organic solvent are added, most compositions become unstable so that different types of emulsifiers are needed. On the other hand, it is preferred to work VOC-free and to a high extent environmentally friendly, so that it is preferred - depending on the use of the metalworking compositions and requirements - to avoid any content, any addition or an amount of petroleum oil or any organic solvent of more than 5 or 3 or 1 % by weight. Further on, for its use as synthetic coolant, the metalworking composition should not contain any petroleum oil or any organic solvent.
  • the aqueous metalworking composition of the invention wherein at least 98 % by weight of the transport component (e) is water, wherein this is calculated such that the whole transport component (e) sums up to 100 % by weight.
  • the water content of the transport agent (e) is higher like e.g. at least 99 % by weight. It is generally desirable to avoid the use of any organic solvents, especially of flammable solvents and solvents classified as volatile organic compounds.
  • the content of the transport agent (e) in the metalworking composition is preferably in a range of from 0.1 to 90 % by weight or in a range of from 1 to 80 % and especially preferred of from 10 to 70 or of from 20 to 60 % by weight.
  • its content in a concentrate is in a range of from 30 to 50 or of from 35 to 45 % by weight.
  • Such compositions show typically a pH in the range of from 6 to 13 or of from 7 to 12.
  • a concentrate does not need to be diluted before its use.
  • the diluted compositions are prepared by adding water.
  • These "dilutions” preferably have a water content in a range of from 20 to 99.5 % by weight or of from 30 to 99 % by weight or more preferred of from 40 to 98 % by weight, of from 50 to 96 % by weight, of from 60 to 94 % by weight, of from 70 to 92 % by weight or of from 80 to 90 % by weight. They often show a pH in the range of from 6.5 to 11.
  • the weight ratio of compounds of component (a) to such of component (b) or of compounds of component (a) to such of component (c) or of compounds of component (a) to such of component (d) is preferably in a range of from 1 : (0.5 to 2) or in a range of from 1 : (0.8 to 1.5) or in a range of from 1 : (0.8 to 1.3) or in a range of from 1 : (0.9 to 1) or nearby to 1 : 1.
  • the same weight ratios are preferably applied for the compounds of component (b) to such of component (c) or of compounds of component (b) to such of component (d).
  • the same weight ratios are preferably applied for the compounds of component (c) to such of component (d).
  • the aqueous metalworking composition of the invention has a weight ratio of compounds of component (a) to such of component (b) to such of component (c) in a range of from 1 : (0.5 to 2) : (0.2 to 3).
  • the weight ratio of compounds of component (a) to such of component (b) to such of component (c) is in a range of from 1 : (0.8 to 1.5) : (0.3 to 1.8) or in a range of from 1 : (0.8 to 1.3) : (0.8 to 1.3) or in a range of from 1 : (0.9 to 1) : (0.9 to 1) or nearby to 1 : 1 : 1.
  • the weight ratio of compounds of component (a) to such of component (b) to such of component (c) and to such component (d) is in a range of from 1 : (0.5 to 2) : (0.2 to 3) : (0.2 to 1.5) or in a range of from 1 : (0.8 to 1.5) : (0.3 to 1.8) : (0.2.5 to 1) or of from 1 : (0.8 to 1.3) : (0.8 to 1.3) : (0.3 to 1.1) or nearby to a range of from 1 : (0.9 to 1) : (0.9 to 1) : (0.4 to 1).
  • the components of the composition are selected and their relative proportions and concentrations adjusted so as to provide a single phase formulation or a two phase formulation.
  • diluted compositions have a total content of compounds (a) to (d) in a range of from 80 to 0.5 % by weight of from 70 to 1 % by weight, of from 60 to 2 % by weight, of from 50 to 4 % by weight, of from 40 to 6 % by weight, of from 30 to 8 % by weight or more preferred of from 20 to 10 % by weight.
  • Table 1 discloses some examples which indicate the more preferred variation of contents in concentrates and dilutions.
  • Table 1 Examples of content of the different components in some concentrates and dilutions according to the invention, wherein (e) is only water Components in % by weight (a) (b) (c) (d) (e) Concentrate 1 30 30 30 5 5 Concentrate 2 30 20 20 10 20 Concentrate 3 15 15 15 15 40 Concentrate 4 10 10 10 10 60 Concentrate 5 8 4 6 2 80
  • the metalworking composition contains or consists essentially of or consists of the following contents of components in a concentrate:
  • the aqueous metalworking composition of the invention may show different features, depending on its specific application and composition.
  • it is especially useful for multi-metal purposes and/or it is an emulsion with an average hydrophobic droplet size of hydrophobic droplets in a range of from 10 to 200 nm especially for the concentrates and which is an emulsion with an average droplet size of hydrophobic droplets in the range of from 10 nm to 30 ⁇ m especially for dilutions.
  • the average droplet size of the metalworking emulsion may be adjusted to a wanted droplet size 1.) in an early stage by variation of the amount and type of emulsifying compound(s) (c) especially by their HLB values and 2.) before application for a metalworking operation by the degree of dilution with more or less water and by using pure or more or less hard water for the dilution. Then it is preferred to adapt the average droplet size to such size of about the average roughness R a of a metallic surface to be metalworked.
  • the degree of lubricity, the stability of the emulsion, the foaming degree, the corrosion resistance and/or the bio-stability are often influenced to better or worse quality. Therefore typically during a metalworking operation, any emulsifying and/or dispersing compound(s) (c) are replenished to the recycled metalworking composition to adjust the emulsification degree and other properties, e.g. as tank side addition.
  • the composition of the invention is a dispersion, emulsion and/or solution at 25 °C.
  • the concentrates as well as the diluents prepared from it are emulsions.
  • at least 95 % by weight of the composition are in a liquid state at 25 °C.
  • these compounds can be at room temperature and at effective working temperature in a range for example of from 10 to 40 °C in the form of a liquid e.g. dissolved in water or a solid, typically at room temperature, although most of them are liquid at room temperature.
  • a compound like KOH can be solid too, but will dissolve easily in water.
  • composition should contain particles like of a wax, these particles or more than 90 % of these are preferably less than 100 nm.
  • the average droplet size may vary between about 5 nm and about 80 ⁇ m. It has been found that droplets of an average droplet size bigger than 50 ⁇ m may lead to instability of the metalworking composition, so that the composition may easily split into two immiscible layers of liquids. It has been found that even average droplet sizes of more than 30 ⁇ m may lead to such instability. On the other hand, there may be a precipitation of any substance added, which may settle down and which precipitation should be avoided as far as possible.
  • the metalworking composition according to the invention is an emulsion.
  • emulsions There are generally two types of emulsions:
  • a concentrate is clear or translucent, it is a micro-emulsion and it is stable. If a concentrate looks hazy or very hazy or milky, the concentrate can be stable or can be unstable. For dilutions, it is not a problem if they do not look clear or translucent, but hazy or very hazy or milky. They may look clear or translucent, but they need not. They do not need to be clear or translucent micro- or macro-emulsions.
  • the aqueous metalworking compositions of the present invention are emulsions, which are as concentrates mostly micro-emulsions and which are as dilutions mostly micro- or macro-emulsions.
  • the dilutions show often a stability such that there is no separation of any phase visible with the naked eye and that there is a clear or translucent micro-emulsion or a transparent, hazy or more or less milky macro-emulsion in a composition diluted with pure water or with hard water of up to 1200 ppm Ca content.
  • the amount of component (a) is increased and/or if the amount of component (c) is decreased, there may sometimes be a change in the consistency of the metalworking composition from micro-emulsions to macro-emulsions; and vice-versa normally too. If the amount of any component (a), (b) and/or (c) is increased or is decreased, there may sometimes be a change in the consistency of the metalworking composition from micro-emulsions to macro-emulsions, too.
  • the metalworking compositions of the present invention comprise or consist essentially of or consist of the following combination of components: [(a1) and/or (a3)] and (b1) and (c3) and (d1) and (e), which are as concentrates preferably micro-emulsions or even clear micro-emulsions and which are as dilutions preferably micro- or macro-emulsions.
  • Each component is herein represented by at least one substance added or contained or both.
  • these components are contained in the following contents in a concentrate: [(a1) and/or (a3)] in a total content in a range of from 10 to 20 % by weight, (b1) in a content of 5 to 10 % by weight, (c3) in a content in a range of from 10 to 20 % by weight, (d1) in a total content in a range of from 5 to 15 % by weight, (e) in a content in a range of from 70 to 25 % by weight and optionally components like any component selected from the group consisting of A to D in a total content of zero or in a range of from 0.01 to 10 % by weight.
  • an emulsion of a concentrate or of a dilution shows an average droplet size predominantly in a range of from 10 nm to 50 ⁇ m or more preferred in a range of from 50 nm to 10 ⁇ m.
  • Reasonable ranges for the average droplet size are often in a range of from 0.15 to 50 microns or of from 0.15 micron to 30 microns.
  • a dispersion shows preferably average particle sizes predominantly in a range of from 10 nm to 10 ⁇ m or more preferred in a range of from 50 nm to 1 ⁇ m.
  • solid compounds that may be present in a metalworking composition as particles a wax, grinding particles and/or lapping particles may be contained. But such solid particulate compounds are used very seldom and typically only in low amount.
  • multi-metal purposes means that the metalworking composition usually has good lubricity on at least two different metallic materials, which may preferably be selected from aluminum, magnesium, titanium, zinc, any of their alloys, brass and steel.
  • a test for the lubricity is only performed on aluminum alloy(s) and steel(s), respectively. This test indicates the usability for different metallic materials well, if the lubricity test on aluminum and on steel gives good results.
  • the aqueous metalworking composition often has a viscosity at 25 °C in a range of from 0.05 to 10 Pa ⁇ s or more preferred in a range of from 0.2 to 3 Pa ⁇ s.
  • composition of the present invention may additionally include, if desired in seldom embodiments, one or more of additives selected from the group consisting of the optional components A to D.
  • the aqueous metalworking composition of the invention may preferably comprise additionally in total 0.002 to 60 % by weight of at least one optional compound selected from the group of optional components A to D.
  • Component A may be contained in a content of 0 % by weight or in a range of from 0.002 to 30 % by weight or preferably in a range of from 1 to 20 % by weight.
  • Component B may be contained in a content of 0 % by weight or in a range of from 0.002 to 5 % by weight in a range of from 0.1 to 2 % by weight.
  • Component C may be contained in a content of 0 % by weight or in a range of from 0.002 to 3 % by weight in a range of from 0.1 to 1.5 % by weight.
  • Component D may be contained in a content of 0 % by weight or in a range of from 0.002 to 30 % by weight or preferably in a range of from 1 to 20 % by weight.
  • the aqueous metalworking composition comprises at least one optional lubricity imparting component A or lubricity imparting compound A, which is a vegetable oil, an animal oil, an ethoxylated, propoxylated or ethoxylated-propoxylated derivative or any combination or any part of any of these, but its content is only contained in the metalworking composition of the present invention in a range of from 1 to 200 % by weight of its content of the component (a), preferably in a range of from 20 to 180 % by weight or of from 40 to 160 % by weight or of from 60 to 140 % by weight.
  • component A is a vegetable oil, an animal oil, an ethoxylated, propoxylated or ethoxylated-propoxylated derivative or any combination or any part of any of these, but its content is only contained in the metalworking composition of the present invention in a range of from 1 to 200 % by weight of its content of the component (a), preferably in a range of from 20 to 180 % by weight or
  • the at least one optional lubricity imparting component A or lubricity imparting compound A may be a water-soluble, a water-dispersible, a water-miscible or a water-insoluble compound.
  • Especially preferred compounds A are the ethoxylated derivatives, which optionally may be compounds contained in any vegetable oil or animal oil or both which is purified, refined, conditioned, chemically modified, synthesized or prepared by any combination thereof.
  • the aqueous metalworking composition comprises at least one biocide B, at least one fungicide B or both.
  • the aqueous metalworking composition of the invention comprises at least one antifoaming agent C and/or at least one defoamer C.
  • the optional component C is preferably selected from polyglycols, siloxanes, polysiloxanes and waxes.
  • organic polymeric material D may be added to or contained in the aqueous metalworking composition of the invention as optional component D.
  • Such organic polymeric material D may predominantly contain or consist of monomers, oligomers, cooligomers, polymers and/or copolymers based on ionomers, acrylamide, acrylic acid/methacrylic acid, butane, epoxide, ethylene, isobutylene, poly- ⁇ -olefine, polyamide, polyglycerols, polyisobutene, propylene, styrene, polysulfonic acid, urethane, their ester(s) and/or their salt(s).
  • the aqueous metalworking composition comprises at least one optional component D, which is based on monomers, oligomers, cooligomers, polymers and/or copolymers of acrylamide, acrylic acid/methacrylic acid, butane, epoxide, ethylene, ionomers, isobutylene, poly- ⁇ -olefine, polyamide, polyglycerols, polyisobutene, propylene, styrene, polysulfonic acid, urethane, their ester(s) and/or their salt(s).
  • optional component D is based on monomers, oligomers, cooligomers, polymers and/or copolymers of acrylamide, acrylic acid/methacrylic acid, butane, epoxide, ethylene, ionomers, isobutylene, poly- ⁇ -olefine, polyamide, polyglycerols, polyisobutene, propylene, styrene, polysulf
  • Preferred organic materials comprise for example: Acrylamide-(meth)acrylate copolymer, ethylene-(meth)acrylate copolymer, styrene-(meth)acrylate copolymer, urethane-carbonate copolymer, urethane-carbonate-... copolymer, urethane-ester-carbonate copolymer, isobutylene-butene copolymer, polysulfonic acid.
  • These organic materials may be sometimes added either as solids, as emulsions or as liquids.
  • Such organic polymeric material D may be helpful for further enhancing the lubricity and at the same time enhancing the bio-stability of the composition.
  • organic polymeric material D in the aqueous metalworking composition may be chosen in a range of from 0.1 to 50 % by weight or in a range of from 1 to 30 % by weight or in a range of from 3 to 15 % by weight or in a range of from 5 to 10 % by weight.
  • the method to prepare an aqueous metalworking composition of the invention is characterized by first adding to water any compounds (b) and (d), then adding any compounds (a) and afterwards then (c), during which mixing procedure until here a heating to temperatures in the range of from 30 to 50 °C and an agitation is used - wherein this mixing succession, heating and agitation are used to get a stable emulsion - and optionally then all other compounds are added.
  • the concentrate prepared may be diluted with water to a wanted dilution degree.
  • the application of the aqueous metalworking composition of the invention may be performed by spraying, high pressure spraying, brushing, roll coating, immersion or other such methods like flowing water.
  • the coated metal substrate may then be metalworked, e.g. cut, ground or machined in the manner desired, wherein the liquid flowing metalworking composition provides a favourable lubricating effect.
  • the method of use of an aqueous metalworking composition of the invention is characterized that the aqueous metalworking composition may be used as a coolant and/or as a lubricant and/or for bending, for blanking, for boring, for broaching, for cooling, for cold forming, for warm forming, for cutting, for drawing, for drilling, for forging, for grinding, for hobbing, for honing, for hydroforming, for lapping, for lubricating, for forming, for milling, for pressing, for punching, for reaming, for cold rolling, for hot rolling, for sawing, for stamping, for tapping, for threading, for turning or for any combination thereof.
  • aqueous metalworking compositions of the present invention show such a high lubricity for very different metallic materials so that they may be excellently used in multi-metal purposes.
  • aqueous metalworking compositions of the present invention show an excellent corrosion protection for very different metallic materials.
  • aqueous metalworking compositions of the present invention show an excellent emulsion stability for the concentrates as well as for the dilutions.
  • aqueous metalworking compositions of the present invention result in clean, shiny and smooth metal surfaces of the finished metallic parts that have been metalworked with this composition.
  • aqueous metalworking compositions of the present invention show nearly all properties to be expected from industry requirements, even typically low-foaming and high bio-stability as well as despite high environmentally friendly compositions like zero-VOC, freedom from alkanolamines and/or freedom from petroleum oils.
  • the aqueous metalworking composition of the invention has preferably a lubricity as measured as average torque number of not more than 300 N ⁇ cm, when measured in a Microtap test with a tapping torque instrument Microtap Megatap II-G8 of Microtap GmbH in Germany.
  • Such tapping torque instrument is often called Microtap instrument.
  • the test may be performed according to ASTM D5619 by drilling into a metal or alloy bar especially into a bar of aluminium 6061 or steel 1018 or both.
  • the Microtap test is not performed exactly according to this standard, but it is used according to the test procedures recommended by the instrument producer for dilutions of 10 % by weight or seldom of down to 5 % by weight.
  • the metal bar usually has pre-drilled holes. The sample of the metalworking composition is added to the hole.
  • a tap will drill through the hole, and the instrument will measure the torque number, using a depth of 14.4 mm, a speed of 660 rpm, a torque of 700 N ⁇ cm and a force of 5 N ⁇ cm for aluminum 6061 bars and using a depth of 14.4 mm, a speed of 500 rpm, a torque of 700 N ⁇ cm and a force of 5 N ⁇ cm for steel 1018 bars.
  • a tap drills through a hole filled with the aqueous metalworking composition, and the instrument output data show an average torque number in N ⁇ cm. Very good data for aluminium and its alloys show ⁇ 200 N ⁇ cm and very good data for steel show ⁇ 230 N ⁇ cm.
  • the aqueous metalworking composition of the invention has preferably a stability such that there is no separation of any phase visible with the naked eye, but a clear or transparent or more or less milky emulsion or any combination thereof in a composition diluted only with pure water or with hard water having a Ca content of up to 1200 ppm Ca. If there is an unstable emulsion, it will split with time and the split will be seen with the eyes. There are two types of stability tests:
  • a stable concentrate can have a clear, transparent or hazy appearance. It does not matter, if it is clear, transparent or hazy, as long as the metalworking composition does not split: Then it is stable. An emulsion can even be more or less milky, but as long as it is stable, it does not matter which appearance a diluted emulsion has.
  • the following stability test methods have been used for concentrates and dilutions, wherein the check of the stability of concentrates or dilutions only by the eyes is still the most common way:
  • the concentrate sample should be stable, which means, it must be clear, transparent or hazy, but there should not be any separation which is seen by the eye.
  • diluted samples For diluted samples: Prepare a 5 % dilution in hard water containing 600 ppm of calcium acetate. Leave the solution at 50 °C in an oven for three days. No separation should be observed, so that the dilution samples appear clear, hazy or milky.
  • the aqueous metalworking composition of the invention has a corrosion protecting effect.
  • the corrosion protecting effect is preferably checked with a cast iron chip test CIC resulting in a corrosion rating of 2 or less if a cast iron bar or more preferred and here used small clean chips are used and tested in contact with a diluted composition of 2 % by weight in deionized water over 24 hours.
  • the test procedure of the cast iron chip test is similar, but few measures are not identical with the data in the standard test methods ASTM D4627 and DIN 51360-2:
  • the chip size is smaller and is of 2 to 3 mm, wherein 2 g of chips and 2 g of aqueous metalworking 5 % dilution in DI-water and 24 hours are used in a petro-dish with cover.
  • the smaller the rating value the better.
  • the worst results show a rating of 5, the best of zero. Starting with a rating value of 3, such aqueous metalworking compositions do not seem to be acceptable for industry.
  • the metalworking composition should not have any corrosive effect on the tool and on parts of the machine in many instances, if the metalworking composition has been tested successfully in a CIC test over 24 hours.
  • the aqueous metalworking composition of the invention is stable against foaming, especially under the specific operating conditions of a metalworking. In several metalworking operations it is wanted that even high pressure spraying cannot cause trouble with foam generation. Further on, foam generated during a metalworking operation should break down after the metalworking operation within 1 minute or less than 1 minute to be a low foaming composition.
  • the metalworking composition is stable against foaming such that there is no longer foam in a foam test as performed in a mixer method in a 1000 ml beaker with 200 ml of a metalworking composition which has 5 % by weight of the concentrate having a concentration of active substances of 5 % by weight in water with a Black and Decker 12-speed mixer at speed 10 for 5 minutes and such that there is then a foam break time of less than 30 seconds for the foam to dissipate.
  • Foam break means total foam dissipation, that is, zero foam on the surface of a solution.
  • the foam test method TM# 2142 is an internal test method. There is no standard method for foam testing. A 5 % dilution means 5 % by weight of a concentrate sample in 95 % DI water. The purpose of this test is to determine the amount of foam generated in a highly agitated system and the time required for that foam to dissipate. Use a 1000 ml Kimax beaker so that the height of the beaker is defined, a 100 ml graduated cylinder, a Black and Decker 12-speed mixer with timer and a stop watch.
  • VOC Test according to EPA24 method: VOC content of a composition is tested according to ASTM D 2369-81, 87, 90, 92, 93, or 95, Standard Test Method for Volatile Content of Coatings. A sample of a metalworking fluid concentrate is placed at 110 °C for at least 60 minutes or until the weight becomes constant to drive out all the water and volatile organic materials. Then VOC content can be calculated by the weight loss in grams/Liter.
  • Test of the average droplet size of an emulsion Test of the average droplet size of an emulsion is measured with an instrument equipped with light scattering technology like Marvern Mastersizer. A light beam or laser beam passes through an emulsion and hits emulsion particles or oil droplets, which scatter the light and change the light intensity. From the light intensity and angle changes, the average droplet size can be calculated.
  • aqueous metalworking compositions for these examples and for further testing these were prepared by first adding to water the selected compounds (b) and (d), then adding the selected compounds (a) and afterwards then the selected compounds (c). During this mixing procedure a heating to temperatures in the range of from 30 to 50 °C and an agitation was used to get an emulsion - and optionally then all other selected compounds were added. On demand, the concentrates prepared were diluted with water to the wanted dilution degree.
  • Table 3 shows a selection for 20 compositions and their properties out of nearly 400 different compositions tested for their lubricity and stability. It was astonishing to identify the different lubricity degrees of the different lubricity imparting compounds tested and to identify the different emulsification degrees of the different emulsifying compounds (c) tested. Further on, it was astonishing that it is not self-understanding that a stable metalworking composition does work well for lubricity on aluminum based metallic materials and on steels at the same time. Therefore, it was necessary to learn how to compose and stabilize a metalworking composition for multi-metal purposes. It was astonishing that it is possible to have a stable, well-lubricating metalworking composition for multi-metal purposes that is still insufficient in corrosion protection.
  • Examples E3, E5, E6 and E17 are inventive examples.
  • Examples E1, E2, E4, E7 to E16, E18 to E20, E26 and E27 as well as CE1 to CE3 are non-inventive examples.
  • Table 3 shows that even hazy and milky metalworking concentrates may show excellent properties, if the emulsion is stable. The visual appearance is not mentioned, if the concentrate or dilution shows clear or translucent appearance. The stability of the concentrate is more important than its visual appearance. All comparison examples show hazy or milky concentrates and all of them are unstable or split, even CE4.
  • the composition of CE1 failed, as it does not have enough emulsifying compounds (c).
  • the composition of CE2 failed, as it does have adequate emulsifying compounds (c), although the compounds (c) have already been increased.
  • the composition of CE3 failed, as it does not have enough adequate emulsifying compounds (c), although even further increased amounts. It is assumed that HLB values of a combination of different emulsifying compounds (c) influence the emulsifying effect, so that not only the amount of any emulsifying compounds (c) is important, but even the chemical characteristics of such compounds are to be selected in a way to stabilize the emulsion. Therefore, specific care has to be taken in an adequate selection of emulsifying compounds (c).
  • Table 4 shows the results of composition C of US 2009/0149359 A1 as indicated in its examples 1 and 2 in comparison to the results of compositions according to the present application.
  • Examples CE4 and E21 to E25 are non-inventive examples.
  • CE4 is the best example of US 2009/0149359 A1 .
  • the pH of CE4 is significantly lower than for E21 to E25.
  • the lubricity measured by tapping torque data for steel of CE4 is in comparison with that of E21 to E25 bad.
  • the corrosion resistance of CE4 too is clearly bad in comparison with that of E21 to E25 as measured in a CIC test.
  • Even the stability of the diluted emulsion of CE4 too is lower in comparison with that of E21 to E25 as measured in an emulsion stability test for dilutions with pure water and/or with hard water.

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Claims (15)

  1. Composition aqueuse de travail de métaux comprenant dans un concentré ou après dilution d'un concentré avec de l'eau dans un diluant :
    • 6 à 40 % en poids de composant (a) qui est un agent lubrifiant comprenant au moins un composé insoluble dans l'eau (a) possédant au moins une chaîne aliphatique hydrophobe et au moins un groupe polaire et possédant une solubilité dans l'eau à 20 °C inférieure à 0,1 g/litre et qui sont choisis dans le groupe de composés constitués par :
    • (a1) des acides gras choisis dans le groupe constitué par l'acide laurique/dodécanoïque, l'acide myristique/tétradécanoïque/myristoléique, l'acide pentadécanoïque, l'acide palmitique/hexadécanoïque/palmitoléique/hex adécapolyénoïque, l'acide margarique/margaroléique, l'acide ricinoléique, l'acide stéarique/octadécanoïque, l'acide linoléique/eicosanoïque, l'acide oléique, l'acide linoléique/linolénique/octadécatétraénoïque ' l'acide arachidique/gadoléique/eicosadiénoïque/arac hidonique/eicosapentaénoïque, l'acide hénéicosanoïque, l'acide béhénique/docosanoïque/érucique/docosapolyé noïque, l'acide docosahexaénoïque et l'acide lignocérique ;
    • (a2) des triglycérides de trois acides carboxyliques identiques ou deux ou trois acides carboxyliques différents à base d'acide oléique, d'acide stéarique, d'acide ricinoléique, d'acide érucique, d'acide lignocérique et/ou d'acide laurique ; et
    • (a3) des dérivés de composés (a1) ou (a2) ou les deux possédant 12 à 5 000 atomes de carbone choisis parmi les dérivés chlorés ou sulfurés, les esters, les éthers, les éthoxylates, les éthoxylates-propoxylates, les propoxylates, les sels de métaux alcalins, les sels de métaux alcalino-terreux et les composés ayant été condensés avec au moins un acide carboxylique ;
    - 0,002 à 40 % en poids de composant (b) comprenant au moins un composé inhibant la corrosion soluble dans l'eau (b) possédant une solubilité dans l'eau à 20 °C de plus de 0,1 g/litre et qui sont choisis dans le groupe constitué par :
    • (b1) des acides monocarboxyliques, des acides dicarboxyliques, des acides tricarboxyliques et des acides polycarboxyliques linéaires et/ou ramifiés, saturés et/ou insaturés possédant au total de 6 à 40 atomes de carbone et possédant des longueurs de chaînes de 4 à 12 atomes de carbone et leurs sels de métal alcalin et sels de métal alcalino-terreux ;
    - 0,002 à 45 % en poids d'au moins un agent émulsifiant et dispersant (c) qui contient au moins un composé émulsifiant et/ou dispersant (c) qui est soluble dans l'eau, miscible à l'eau ou dispersible dans l'eau et qui est choisie dans le groupe constitué par des tensioactifs non ioniques, anioniques et zwitterioniques constitué par
    • (c1) des alcools d'alkyle éthoxylés, des alcools d'alkyle éthoxylés-propoxylés, des alcools d'alkyle éthoxylés comportant un coiffage de groupe terminal et des alcools d'alkyle éthoxylés-propoxylés comportant un coiffage de groupe terminal, et le groupe alkyle des alcools d'alkyle étant saturé ou insaturé et possédant un nombre moyen d'atomes de carbone dans la plage de 4 à 24 et possédant soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée ;
    • (c2) des alkylphénols éthoxylés, des alkylphénols éthoxylés-propoxylés, des alkylphénols éthoxylés comportant un coiffage de groupe terminal et des alkylphénols éthoxylés-propoxylés comportant un coiffage de groupe terminal, le groupe alkyle des alkylphénols - saturé ou insaturé - possédant un nombre moyen d'atomes de carbone dans la plage de 4 à 18 et possédant soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée ;
    • (c3) des acides alcanoïques éthoxylés ou éthoxylés-propoxylés, des acides gras éthoxylés ou éthoxylés-propoxylés et/ou d'autres acides organiques éthoxylés ou éthoxylés-propoxylés, et les acides d'alkyle possédant un radical alkyle - saturé, insaturé et/ou cyclique - qui possède un nombre moyen d'atomes de carbone dans la plage de 4 à 24 et possédant soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée ;
    • (c4) des copolymères à bloc contenant au moins un bloc de poly(oxyde d'éthylène) et au moins un bloc de poly(oxyde de propylène) ainsi que des copolymères statistiques, et les copolymères à bloc possédant un bloc de poly(oxyde d'éthylène) qui comprend un nombre moyen de 2 à 100 motifs d'oxyde d'éthylène et un bloc de poly(oxyde de propylène) qui comprend un nombre moyen de 2 à 100 motifs d'oxyde de propylène ;
    • (c5) des alkyl-polyglycosides dont le groupe alkyle - saturé ou insaturé - possède un nombre moyen d'atomes de carbone dans la plage de 4 à 18 et soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée, et possède une moyenne de 1 à 5 motifs d'au moins un sucre, les motifs du ou des sucres étant liés de manière glycosidique au groupe alkyle, le terme « sucre » étant compris comme comprenant tous les saccharides et/ou les autres composés de type sucre ;
    • (c6) des tensioactifs anioniques dont le groupe alkyle - saturé ou insaturé - possède un nombre moyen d'atomes de carbone dans la plage de 4 à 24 et soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée, dans lesquels il y a au moins un groupe sulfate ou sulfonate présent dans la molécule ;
    • (c7) des sulfates d'éther dont les alcools d'alkyle éthoxylés ou les alcools d'alkyle éthoxylés-propoxylés possèdent un groupe sulfate, le groupe alkyle des alcools d'alkyle
    - saturé ou insaturé - possédant un nombre moyen d'atomes de carbone dans la plage de 4 à 24 et soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée, la chaîne d'oxyde d'éthylène possédant un nombre moyen de 2 à 30 motifs d'oxyde d'éthylène et la chaîne d'oxyde de propylène possédant un nombre moyen de 1 à 25 motifs d'oxyde de propylène ;
    • (c8) des phosphates d'éther dont les alcools d'alkyle éthoxylés ou les alcools d'alkyle éthoxylés-propoxylés possèdent un groupe phosphates, le groupe alkyle des alcools d'alkyle - saturé ou insaturé - possédant un nombre moyen d'atomes de carbone dans la plage de 4 à 24 et soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée, la chaîne d'oxyde d'éthylène possédant un nombre moyen de 2 à 30 motifs d'oxyde d'éthylène et la chaîne d'oxyde de propylène possédant un nombre moyen de 1 à 25 motifs d'oxyde de propylène ;
    • (c9) des esters de phosphate dont un ou deux groupes alkyle - saturé ou insaturé - possèdent indépendamment l'un de l'autre un nombre moyen d'atomes de carbone dans la plage de 4 à 24 et soit une structure de chaîne linéaire, soit une structure de chaîne ramifiée, dans lesquels il y a un groupe phosphate présent dans la molécule ;
    • (c10) des monoglycérides éthoxylés, propoxylés, éthoxylés-propoxylés ou éthoxylés notamment avec des groupes terminaux fermés ;
    • (c12) des amines grasses ainsi que des amines grasses éthoxylées, propoxylées, éthoxylées-propoxylées ou éthoxylées avec des groupes terminaux fermés ;
    • (c13) un sorbitane et des sorbitanes qui sont éthoxylés, propoxylés, éthoxylés-propoxylés ou éthoxylés avec des groupes terminaux fermés ;
    • (c14) l'acide succinique et leurs esters et sels ;
    - 0,002 à 30 % en poids d'un agent d'alcalinité (d) contenant au moins un composé soluble dans l'eau alcalin (d) choisi dans le groupe constitué par des hydroxydes et des carbonates ; et
    - au moins 0,004 % en poids d'un composant de transport (e), au moins 98 % en poids du composant de transport (e) étant de l'eau,
    l'agent lubrifiant (a) contenant au moins deux ou au moins trois ou au moins quatre composés (a) différents, le rapport en poids de composés du composant (a) sur ceux du composant (b) sur ceux du composant (c) étant dans une plage allant de 1 : (0,5 à 2) : (0,2 à 3).
  2. Composition aqueuse de travail de métaux selon la revendication 1, la composition de travail de métaux contenant les teneurs suivantes de composants dans un concentré : (a) en une teneur dans une plage allant de 10 à 20 % en poids, (b) en une teneur de 5 à 10 % en poids, (c) en une teneur dans une plage allant de 10 à 20 % en poids, (d) en une teneur dans une plage allant de 5 à 15 % en poids, (e) en une teneur dans une plage allant de 70 à 25 % en poids et éventuellement des composants en une teneur totale de zéro ou dans une plage allant de 0,01 à 10 % en poids.
  3. Composition selon la revendication 1 ou 2, qui est une dispersion, une émulsion et/ou une solution à 25 °C et dont au moins 95 % en poids de la composition sont dans un état liquide à 25 °C.
  4. Composition selon l'une quelconque des revendications 1 à 3, dont le pH est dans la plage allant de 5 à 13.
  5. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 4, qui est une émulsion dotée d'une taille moyenne de gouttelette hydrophobe de gouttelettes hydrophobes dans une plage allant de 10 à 200 nm pour les concentrés et qui est une émulsion dotée d'une taille moyenne de gouttelette hydrophobe de gouttelettes hydrophobes dans une plage allant de 10 nm à 30 µm pour des dilutions, la taille moyenne de gouttelette de l'émulsion étant mesurée avec un instrument muni d'une technologie de diffusion de lumière comme un Mastersizer de Malvern.
  6. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 5, qui possède un pouvoir lubrifiant tel que mesuré comme un nombre moyen de couple non supérieur à 300 N.cm, lorsqu'il est mesuré dans un essai de Microtap avec un instrument à couple de taraudage Microtap Megatap II-G8 de Microtap GmbH.
  7. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 6, qui possède une stabilité telle qu'il n'y a pas de séparation d'une quelconque phase visible à l'œil nu et qui est une micro-émulsion limpide ou translucide ou une macro-émulsion transparente, trouble ou plus ou moins laiteuse dans une composition diluée avec de l'eau pure ou avec de l'eau dure d'une teneur en Ca allant jusqu'à 1 200 ppm.
  8. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 7, la teneur du composant (a) étant contenue en une plage allant de 6 à 28 % en poids.
  9. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 8, le composant d'inhibition de la corrosion (b) contenant au moins deux ou au moins trois ou au moins quatre composés (b) différents, notamment pour optimiser la protection contre la corrosion.
  10. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 9, le composant (b) étant contenu dans une plage allant de 0,01 à 28 % en poids.
  11. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 10, l'agent d'alcalinité (d) étant choisi parmi des hydroxydes et des carbonates de métaux alcalins et de métaux alcalino-terreux.
  12. Composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 11, l'agent d'alcalinité (d) étant contenu en une plage allant de 0,01 à 15 % en poids ou allant de 0,1 à 12 % en poids ou allant de 1 à 10 % en poids ou allant de 3 à 12 % en poids.
  13. Procédé de préparation d'une composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 12 en ajoutant d'abord à de l'eau de quelconques composés (b) et (d), puis en ajoutant de quelconques composés (a) et après alors (c), durant laquelle procédure de mélange jusqu'à présent, un chauffage à des températures dans la plage allant de 30 à 50 °C et une agitation sont utilisés, et éventuellement ensuite tous les autres composés sont ajoutés.
  14. Utilisation d'une composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 12 en tant qu'agent de refroidissement, comme lubrifiant et/ou pour le cintrage, pour le découpage, pour l'alésage, pour le brochage, pour le refroidissement, pour la coupe, pour l'étirage, pour le perçage, pour le formage à froid, pour le formage à chaud, pour le forgeage, pour le meulage, pour le taillage, pour le rodage, pour l'hydroformage, pour le rodage, pour la lubrification, pour le formage, pour le fraisage, pour l'emboutissage, pour le poinçonnage, pour l'alésage, pour le laminage à froid, pour le laminage à chaud, pour le sciage, pour l'estampage, pour le taraudage, pour le filetage, pour le tournage ou pour une quelconque combinaison correspondante.
  15. Processus de travail de métaux caractérisé en ce que l'opération de travail de métaux est réalisée par rinçage, pulvérisation, pulvérisation à haute pression, brossage, écoulement, cannelure, revêtement au rouleau, immersion ou une quelconque combinaison correspondante avec la composition aqueuse de travail de métaux selon l'une quelconque des revendications 1 à 12.
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KR20140043375A (ko) 2014-04-09
MX2013014267A (es) 2016-10-03
MX358939B (es) 2018-09-10
JP5968428B2 (ja) 2016-08-10
ZA201308327B (en) 2015-03-25
WO2012152639A1 (fr) 2012-11-15
CA2835019A1 (fr) 2012-11-15
CN103827278A (zh) 2014-05-28
BR112013028516A2 (pt) 2017-01-10
CN109401810B (zh) 2022-03-18
KR101993485B1 (ko) 2019-06-26
CN109401810A (zh) 2019-03-01
US20140128299A1 (en) 2014-05-08
EP2705128A1 (fr) 2014-03-12
CA2835019C (fr) 2018-04-10
ES2935302T3 (es) 2023-03-03
JP2014513189A (ja) 2014-05-29

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