MXPA99002070A - Novel water soluble metal working fluids - Google Patents

Abstract

This invention relates to novel water soluble metal working fluid compositions, their use to work metal, a process for working metal using such compositions and the metal worked article of manufacture. More particularly, this invention relates to fluid compositions useful in cutting, grinding, shaping and other metal working operations which require a lubricant. The terms"first Group A"and"second Group B"are used herein to denote different groups and not to indicate any sequence of use or selection as any possible combination or sequence of use of a component(s) is envisioned without limit of any kind. The disclosed fluid compositions are also anticorrosive and environmentally more acceptable than current oil based fluids. There has now been discovered an essentially odorless, substantially non-oil misting, water-soluble metal working fluid comprising at least one component selected from a first Group A herein and optionally one or more components selected from a second Group B herein preferably with the balance of the composition being water and other (optional) minor ingredients. When a component is employed from Group A and a component is employed from Group B the action of the combination generally enhances performance of the resulting combination with contain moieties from both Group A and Group B.

Description

NOVEDOS HYDROSOLUBLE FLUIDS FOR WORKING METALS BACKGROUND OF THE INVENTION The work of a metal using a tool to work it is a practice that has been carried out for years. Fluids of the prior art have been used to facilitate such work with metals. However, previously known oil-containing metalworking fluids require reuse or disposal that is not discharged into common sewage treatment systems. In some cases, the cost of the waste has become such a cost that it approaches the initial cost of the fluid. Without being limited by theory, it is believed that fluids for metal working satisfy one or more functions in various metal working applications. Typically, such illustrative non-limiting functions include the removal of heat from the workpiece and tool (cooling), the reduction of friction between fragments, the tool and the work piece (lubrication), the removal of metal residues produced by the work, the reduction or inhibition of corrosion, and the prevention or reduction of accumulation on edges as well as between the workpiece and the tool. In this way, these one or more functions normally require a formulation or combination of components in the lubricating fluid to achieve the best attributes necessary for a particular metal working operation. References for metal work that describe an illustrative range of metalworking operations include The 12th American Machinist Inventory of Metal orking Equipment 1976-78, American Machinist, December 1978 and November 1983; McGraw-Hill, Inc. 1221 Avenue of the Americas, New York NY 10020; Lubricants, Cutting Fluids, and Coolants; Wilber J. Olds, Cahners Books, 89 Franklin Street, Boston, MA. 02110; TRIBOLOGY IN METAL WORKING, Friction, Loubricant and Wear, John A. Schey, Professor, Department of Mechanical Engineering, University of Waterloo, Ontario, Canada, American Society for Metals, Metals Park, Ohio 44073. The above three references are incorporated in the present in its entirety as a reference. A number of fluids have recently been proposed that substitute fluids for working metals containing oil, such as primary amides, ethylenediaminetetraacetic acid, fatty acid esters and alkanolamine salts. Said compounds can be replenished during use by dissolving tablets containing said compounds during the useful life of the fluid. See the US patent. 4,144,188 a'SatO. It has also been found that some amines are useful in cutting oils as antibacterial agents. Said amines include alkanolamine and arylalkylamine such as p-benzylaminophenol. See EPO 90-400732 to Noda et al. As mentioned above, one of the problems that occur in the industry is the proper disposal of fluids to work metals. The amines mentioned above are removed from the fluids by biodegradation, necessitating installations such as settling tanks, treatment tanks and silt treatment tanks. Said system is described in Japanese patent 03181395. Other methods of waste disposal systems and oil removal are used to comply with environmental standards. Worker safety can be an aspect with the fluids to work water-soluble metals that contain oil currently used. These fluids inevitably come into contact with workers who use fluids in cutting, bending, threading or other metalworking applications. Said fluids having oil can create a mist at the place where the workpiece is being worked or when the fluid is sprayed, and said mist travels through the air in the vicinity of the machine and the operator thereof. Some attempts have been made to reduce the problem of fog formation such as those mentioned in British Patent 2,252,103. Therein is disclosed a polymeric thickener comprising a copolymer of acrylamide, sodium acrylate and N-n-octylacrylamide. The copolymer is formulated with water-insoluble and soluble monomers.

Due to the formation of fog and dispersion of it in the workplace when some fluids are used to work water-soluble metals commonly used, a distinctive odor that permeates the entire area is almost always associated with said workplace. Normally said odor is not pleasant and is tolerated as a condition that is unavoidable. There is a need for a water-soluble metal working fluid that does not form oil mist and odorless, particularly useful for cutting operations. There is also a need for a fluid that avoids the need for waste costs, and that provides the workplace with a more sanitary and acceptable atmosphere in which to work.

OBJECTS OF THE INVENTION An object of the invention is to provide an improved lubricant composition that is used in metal working environments. Another object of the invention is to provide an improved lubricant composition that is effective with and without the use of a phosphate or phosphonate, or borates. A further object of the invention is to provide an improved lubricant composition that is effective with the use of phosphorus-containing compounds.

It is also an object of the invention to provide an improved lubricant composition useful in extreme pressure applications. A further object of the invention is to provide an improved lubricant composition containing a lubricant-imparting component containing a carboxylate portion and a phosphorus portion within the same molecule. Still another object of the invention is to provide an improved lubricant composition that is effective when used with borate compounds. It is another object of the invention to provide an improved lubricant composition containing a lubrication imparting mixture in which a component contains an amide and the same or a second component contains a phosphorus portion. Yet another object of this invention is to provide an improved lubricant composition containing manufactured and natural polymers such as proteins used with or without a phosphorus portion or borate portion to provide lubrication at extreme pressures and additionally a simple or boundary lubrication. These and other objects are satisfied in the present invention, of which a non-limiting description is given below.

BRIEF DESCRIPTION OF THE INVENTION It has now been discovered a water-soluble metalworking fluid, substantially non-oil-mist and odorless, useful for a variety of metal working operations, including without limitation, cutting, abrasion, forming and the like, comprising at least one selected component of a first group A herein and optionally one or more components selected from a second group B herein - preferably the balance of the composition being water and other minor ingredients (optional) When a component of group A is employed and a component of group B is employed, the action of the combination generally improves the performance of the resulting combination. If desired, more than one component of group A and / or group B can optionally be used depending on the specific application, or in addition, if desired, one component of group A can be an adduct of components of group A and group B with which resulting component adduct that provides improved lubrication contains a portion of carboxylate and phosphorus within the same molecule. The invention comprises a method for working metals comprising providing as a lubricant to said metal, an effective lubricating amount of a fluid lubricating composition comprising one or more water-soluble components selected from: a first group (A) comprising: amides; polyamides; polyamino acids, salts and esters; one or more monocarboxylic acids having one to six functionalized or non-functionalized carbon atoms, examples are: Cl-C 20 sulfone alkoxy, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that this does not include 2-hydroxybutyric acid and 3-hydroxybutyric acid; polycarboxylic acids, salts or their esters; amino acids, salts and esters; sulfonic acids and salts; a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide; mercaptocarboxylic acids, salts and esters; keto acids; organo-acids substituted with amine; amino acids substituted, salts and esters; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids, or their salts; organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids or their salts, and additionally a portion selected from sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester , amide, amine, ether, sulfide, disulfide or aryl; alone or optionally with one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites and hypophosphites; composition that provides a synergistic lubricating effect or added functionality when used with one or more components of group (A) and group (B). In one embodiment, the composition comprises one or more reaction products of said composition associated with a component or components thereof or the application of said composition to a metal being worked. The lubricants employed herein have a lubricating property selected from the group consisting of extreme pressure, boundary lubricant, single or antiwear film, or combinations thereof. If it is more preferred to employ a phosphate as a component of group B of this invention together with a polyamino acid or polycarboxylate or amide or polyamide or amino acid as a component of group A.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1-18 are graphs illustrating the working performance of metals of the compositions of this invention in various laboratory tests.

DETAILED DESCRIPTION OF THE INVENTION Suitable components of group A include, but are not limited to, carboxylic acids such as monocarboxylic acids having one to six functionalized or non-functionalized carbon atoms, examples being alkoxy cl ~ c20 'sulfone, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that these do not include 2-hydroxybutyric acid and 3-hydroxybutyric acid; hydroxycarboxylic acid or a salt thereof, and polycarboxylic acids, such as acids, partially neutralized acids or salts whose carboxylic acids can be conveniently represented by the formulas R! C02H (I) wherein in relation to the formula (I), R_ is Hydrogen or alkyl of C? _g, or R] _ is RaORfc, where Ra is linear or branched alkyl of Cg_2o and Rb is linear or branched alkylene of C? _Cg, or Ri is RCSR (¿, wherein Rc is C? _20 'and Rd is alkylene or hydroxyalkylene of C__g, with the proviso that these acids are not 2-hydroxybutyric or 3-hydroxybutyric acid, and where in relation to formula (II), R2? (CHx) mCHC02H] n (CHy) or R3 (II) R2 and R3 are selected as the same or different, and may independently be hydrogen or oxygen, or an organic group including alkyl, aryl, mercapto, thio or dithioorganic, hydroxy, hydroxyalkyl, alkenyl, alkoxy, alkoxyalkyl or aromatics when used in the formula (II); and is numerically an independent integer, either 1 or 2; m is zero to about 40; or is approximately zero to about 18; and n is 1 to about 5,000 to 7,000 or more; m is zero at about 30 and m, o and n are integers independent, except that Rj_ can not be 3-carboxypropyl or an alkyl substituted with carboxymethyl. As used herein, the term "alkyl" includes but is not limited to C 1 -C 30 alkyl, substituted and unsubstituted alkyls, linear and branched, functionalized and non-functionalized, and also includes alkyl ethers and alkyl polyethers, mixtures thereof and similar. Those skilled in the art will recognize upon reading this description that the lengths of the alkyl chain of more than 30 may be employed. As used herein the term "aryl" includes, but is not limited to, phenyl, substituted phenyl, biphenyl, and diphenyl ether, mixtures thereof, and the like. Subindexes such as m, n, o, x and y, are conveniently used herein and are integers that vary independently from formula to formula and within formulas. The structure formulas employed herein are used to illustrate the different components and are not designed to limit the invention. Illustratively, non-limiting examples of carboxylic acids and salts useful herein include formic acid, dithiodipropionic acid, polyacrylic acid, thioglycolic acid, lactic acid, 1,2,3,4-butanetetracarboxylic acid, oxalic acid, malonic acid, acid succinic, glutaric acid, adipic acid, dodecanedioic acid, glycolic acid, glyoxylic acid, glyceric acid, propanetricarboxylic acid, tricarboxyhexane, acid tartaric acid, ricinoleic acid, lactic acid, 3-dodecyloxypropionic acid, 3-octyloxypropionic acid, phosphonobutanetricarboxylic acid, and salts thereof, mixtures thereof and the like. Other useful non-limiting carboxylic acids include the group comprising N-phonomethylglycine and water-soluble salts and esters; lactic acid, formic acid, glycolic acid, glyoxylic acid, glyceric acid, octylthiobutyric acid, octylthiopropanoic acid, octyloxypropanoic acid, decyloxypropanoic acid, dodecyloxypropanoic acid, 4-methylthio-2-hydroxy-butyric acid, and salts and esters thereof and mixtures thereof and the like, and is a polycarboxylic acid selected from the group consisting of polyacrylic acid, butanetetracarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, undecanodioic acid, propane tricarboxylic acid, tartaric acid, sebacic acid, maleic acid, fumaric acid, citric acid, itaconic acid, citraconic acid, tartaric acid, malic acid, aconitic acid, and brazilic acid and tricarboxyhexanes and salts and esters thereof and the like . By way of illustration, non-limiting examples of salts of carboxylic acids useful herein include, but are not limited to, those such as the alkali metal, ammonium and phosphonium salts, mixtures thereof and similar, including sodium, potassium and the like and mixtures thereof. Also useful are carboxylic acids containing two or more carboxylate moieties, if desired. The carboxylic acid can be a polymer with repeating units having caboxylate groups. Exemplary suitable amino acids useful herein as a component of group A include, but are not limited to, both the naturally occurring amino acids and the synthetic amino acids manufactured containing at least one each of a carboxylic acid group and an amine group and which are conveniently represented by the formulas: R4 (CHNH2C02H) r (III) R5 [(CHx) m (CHNH2C02H) n] o (CHy) pR6 (IV) R5 [CHX) m (CHNH2 (CH2) zC02H) n ] 0 (CHy) pR6 (VAT) where R4, R5 and R? in the formulas (III) and (IV) are with the same or different independently, and can independently be hydrogen, alkyl or aryl; carboxyl; carboxymethyl; hydroxyalkyl or amine or sulfur; or mercaptan; lots of phosphorus; x, y, yz as used in these formulas (III) and (IV) are the same or different independently, and any are 1 or 2, m and p are used in these formulas if they are the same or different independently and are on the scale from 0 to 6, and r is an integer that varies independently from 1 to 10. However, ny or they must be at least 1, but they can be whole from 1 to 6 independently, salts or esters thereof. Useful and typical non-limiting examples of suitable amino acids useful for the practice of this invention include acidic amino acids, basic amino acids, neutral amino acids and mixtures thereof, which are conveniently representative also of the group described above. The methionine hydroxyl analogue or a salt thereof is an amino acid useful herein. Acceptable non-limiting acidic amino acids typically useful for carrying out the practice of this invention include aspartic acid, including L-aspartic acid, D-aspartic acid and D, L-aspartic acid; and glutamic acid including L-glutamic, D-glutamic, D, L-glutamic; N-phosphonomethylglycine, its salts and esters, N, N-di (2-carboxymethyl) -N-methylphosphonic acid and mixtures thereof and the like. Those skilled in the art will know that for the purposes of working with metals the optical activity is not important, which means that the D, L, meso, racemic and other isomers work equally well. The monocarboxylic acids having one to six carbon atoms functionalized or non-functionalized as an example, are C 1 -C 20 alkoxy sulfone, alkylene phosphonates, sulfur, functionalized amine and the like, salts and esters, with the condition that these do not include 2-hydroxybutyric acid and 3-hydroxybutyric acid, and hydroxycarboxylic acids or salts thereof show lubrication at extreme pressures. Typically acceptable non-limiting examples of useful amino acids herein include arginine, histidine, tryptophan, ornithine, mixtures thereof and the like. Whenever when lysine, an amino acid, is used as a component of group A, then a borate may be used as a component of group B. Illustrative, non-limiting examples illustrating sulfur group A amino acids which are useful herein to carry out this invention includes cysteine, cystine, methionine, hydroxymethionine analogue, homocysteine, felinin, isovaltin, penicillamine, vitamin-U, methyl methionine sulfone chloride, mixtures thereof and salts thereof and the like. Other useful non-limiting amino acids which may be employed herein by way of illustration include, but are not limited to, an amino acid or salts thereof, a basic amino acid, a natural amino acid or salts or mixtures thereof. Alanine, tyrosine, asparagine, valine, glutamine, glycine, hydroxyproline, isoleucine, leucine, phenylalanine, serine, threonine, thyroxine, phosphoserine, norleucine, norvaline, mixtures thereof and salts thereof and the like can be used herein.

Useful acidic amino acids comprise aspartic and glutamic acid, isomers and racemic forms thereof, and N, N- (2-carboxymethyl) N-methylphosphonic acid, N-phosphonomethylglycine, salt and ester derivatives, O-phosphoserine, and mixtures thereof thereof. Useful basic amino acids comprise a basic amino acid selected from the group consisting of arginine, histidine, ornithine and tryptophan, and mixtures thereof and the like. Illustratively, useful non-limiting amides of group A which may be employed herein include those amides and polyamides which are water-soluble as the compound or as their salt, and wherein the nitrogen may be substituted or unsubstituted, and some of which are represented conveniently with the formula: R7C0NR8R9 (V) wherein R7, R1 and R9 as used in the formula (V) can independently be hydrogen, alkyl, aryl, a functionalized alkyl or functionalized aryl groups, NH, N, N, N llRl2 'wherein io »Rll and R12 may be the same or different, and are independently hydrogen, alkyl, functionalized alkyl groups, aryl or functionalized aryl groups, and are functionalized groups containing alkylaryl groups, with the proviso that Rg and Rg they may not be polyethyleneimine, wherein R7 is M00C (CH2) g-, Rg and R may not be C4-4 hydroxyalkyl, and wherein R7 is C- \ 2-1 alkyl > ? R8 and Rg can not be hydroxyethyl. Moreover, if one of Rg and Rg is H and the other is C3-30 alkyl, then C7 may not be selected from -CH2CH2C00H, -CH = CHC00H, or orthocarboxyphenyl. When one of Rg or Rg is H, and the other is CH2CH2CH2CH (NH) COOH, then R7 may not be an alkyl group containing from 8 to 22 carbon atoms. The polyamides include both molecules that contain two or more amide groups and polymers in which the amide moieties are contained in the repeating units, wherein M is as used above, and vary independently of formula to formula throughout. this description, but are defined as in formula XI, page 15. Useful and non-limiting examples of "functionalized alkyl" include 4-caboxbutyl, 4-butyl-1-sulfonic acid, 4-phosphonobutyl aspartyl, mixtures thereof and Similar. Non-limiting examples of acceptable amides useful for the practice of this invention include, but are not limited to, asparagine, maleic acid, urea, biuret, polyasparagine, guanidine, glutamine, polyurea, poly (2-ethyl-2-oxazoline), N , N-dimethylacetamide, oleoamide, polyvinylpyrrolidone, pyroglutamic acid, polyacrylamide, polylactams, N-cocoylglutamate, nonilamidoadipic acid, 4-nonylamidobutylsulfonic acid, or a salt or mixtures thereof and the like.

As used herein, the term amide and polyamides includes, but is not limited to, those amides and polyamides which may be salts of a molecule containing an amide or a polyamide or a mixture thereof, and esters of the molecule and salts partial also. Non-limiting and illustrative examples are polyacrylamides, polyoxazolines and maleamic acid, which can be used as a component of group A. Without being limited by theory, it is believed that propellants such as mono- and diammonium maleate, can be converted to maleic acid at temperatures of work. Illustratively, naturally occurring sulfur compounds of group A useful herein include those such as amino acids cysteine, cystine, methionine, homocysteine, feline, penicillamine, isovaltine, vitamin U and manufactured products and mercaptocarboxylic acids such as mercaptosuccinic acid, dimercaptosuccinic acid, 2-mercaptopropionic acid and mercaptoacetic acid and the like which are water-soluble either as the compound or its salt, are useful for the practice of this invention. Illustrative and non-limiting examples of group A organosulfonates useful herein include the alkylbenzene sulphonate salts wherein the alkyl and / or the phenyl ring may or may not be substituted with functional groups such as: wherein R22 in the formula (VII) can independently be alkyl, substituted alkyl, alkoxy, hydrogen, aryl aminoalkyl, amine, carboxyl, hydroxyl or amide, and M is independently hydrogen, alkali metals, ammonium and organoammonium and mixtures thereof, a salt of the same and similar. Examples of non-limiting organosulfonates useful for practicing this invention include the alkali metal or ammonium salts of 4-octylbenzenesulfonic acid, 2-octylbenzenesulfonic acid, 3-octylbenzenesulfonic acid, 4-nonylbenzenesulfonic acid, 2-nonylbenzenesulfonic acid, 3-nonylbenzenesulfonic acid, 4-decylbenzenesulfonic acid, 2-decylbenzenesulfonic acid, 3-decylbenzenesulfonic acid, 4-undecylbenzenesulfonic acid, 2-unidecylbenzenesulfonic acid, 3-undecylbenzenesulfonic acid, 4-dodecylbenzenesulfonic acid, 2-dodecylbenzenesulfonic acid, 3-dodecylbenzenesulfonic acid and similar compounds which contain different alkyl chain lengths, mixtures thereof and the like. If desired, sodium or potassium sulfide or sodium or potassium hydrogensulfide, or mixtures thereof, may be used as a component of group A in the practice of this invention. '* Other useful illustrative components of group A include but are not limited to, derived protein masses of natural and manufactured animals and vegetables such as animal-derived glues and albumins such as albumin are whey (from the blood), ovalbumin (from egg whites), lactalbumin (from milk), bovine serum albumin (BSA), somatotropin of bovine (bST), 1,2-dithia-5, 8, 11, 14, 17, 20, 23,26-octaazacyclononacosane and globulins such as those derived from animal sera, and casein. Additional examples include skin collagen, proteins derived from tendons and bones, elastins from tendons and arteries, and hair keratin from nails and horns. Other examples of proteins include glycoproteins, phosphoproteins and chromoproteins, mixtures thereof, a salt or salts thereof and the like. Illustrative examples of proteins or polypeptides which are polyamino acids or salts or esters thereof useful herein as a component of group A are polyamino acids which are those polyamino acids including single amino acid homopolymers, block or random copolymers of one, two or more amino acids, mixtures thereof and the like, and which include but are not confined to natural or synthetic proteins or oligopeptides or polypeptides. Moreover, the illustrative amino acids can be natural or synthetic, D-, L- or racemic forms available either through synthesis or from natural protein sources, both animal and plant, which are water-soluble either as the polymer free or as a salt, and which are conveniently described by the following representative schematic formula: H [NH (CR23R24) mC0] n0H (VIII) wherein m as used in this formula (VIII) is an integer that varies independently from 1 to 12, n is a whole which varies independently from 2 to about 2000, such that the amino acid remains water-soluble, R23 and R2 as used in this formula (VIII) are the same or different and vary within a polymer chain and for example consist independently of hydrogen or -C02H, -CH2C02H, -CH2CH2C0H, -CH3, -CH2CH3, CH2CH2CH3, -CH2CH2CH2CH3, -CH (CH3) 2, CH2CH (CH3) 2, - (CH2) QX where o is 0 to 20 and X is any of R23, -OH, -SH, -SSCH2CH (NH2) C02H, -SCH3, phenyl, tolyl, hydroxyphenyl, guanidinyl, pyrrolidinyl, NH2, imidazoyl, indolyl, acetoa gone, and mixtures thereof and the like. Non-limiting examples of suitable and useful polyamino acids include polyglutamic acid, polyasparagine, polyaspartic acid and polyaspartic / glutamic copolymers, polyproline or a proline copolymer with another amino acid or a salt or salts thereof. The non-limiting and illustrative sulfonic acids may be employed as a component of group A of this invention, including those of the formula: R27S02R28G (X) wherein R27 is selected from linear or branched alkyl, alkenyl, alkoxy and alkylamino groups, substituted or not substituted which have 6 to 20 carbon atoms and optionally contain one or more oxygen atoms, and R2g is absent or selected from linear or branched, substituted or unsubstituted alkylene or alkenylene, alkoxy and alkylamino groups containing 1 to 6 atoms of carbon and optionally containing one or more oxygen atoms, and G is selected from -C0M, -0S03M, -S00M, 0P0 (0M) 2, or -P0 (0M) 2 wherein M in relation to this is H , an alkali metal cation, alkaline earth metal or ammonium cation. Non-limiting examples of sulfone acids useful for practicing the invention as a component of group A include the alkali metal or ammonium salts of octylsulfonylpropionic acid, dodecylsulfonylbutyric acid, dodecylsulfonylpropionic acid, N-octylsulfonyl-beta-alanine and nonilaminosulfonylpropionic acid . The non-limiting and illustrative keto acids of the formula 29C (= O) R30G (XI) are useful herein as a component A, wherein R2g is selected from hydrogen, linear or branched, substituted or unsubstituted alkyl, alkenyl and alkoxy groups having 6 to 20 carbon atoms and optionally containing one or more oxygen atoms, and R3u is absent or selected from hydrogen, linear or branched, substituted or unsubstituted alkylene or alkenylene and alkoxy groups containing 1 to 6 atoms carbon and which optionally contain one or more oxygen atoms, and G is selected from -C02M, -OS0 M, -S020M, 0P0 (0M) 2, or -P0 (0M) 2 wherein M is H, (hydrogen), alkali metal cation, metal cation alkaline earth and organoammonium, ammonium, mixtures thereof and the like. Illustrative and non-limiting examples of keto acids useful in practicing this invention include the alkali metal or ammonium salts of octylsuccinate, decyl succinate, dodecyl succinate and 5-oxo-hexadecanoic acid, mixtures thereof and the like. The non-limiting and illustrative amine-substituted organo acids of the formula: R31N (R33) R32G (XII) are useful herein as a component of group A, wherein 3 is selected from hydrogen, linear or branched alkyl, alkenyl and alkoxy groups , substituted or unsubstituted having 6 to 20 carbon atoms and optionally containing one or more oxygen atoms, and R32 is absent or selected from hydrogen, linear or branched, substituted or unsubstituted alkylene or alkenylene, alkoxy and alkylamino groups; containing 1 to 6 carbon atoms and optionally containing one or more oxygen atoms, and R33 is selected from H, linear or branched, substituted or unsubstituted alkyl or alkenyl groups having 6 to 20 carbon atoms and optionally containing one or more oxygen atoms, and G is selected from -C02M, -0S03M, -S020M, 0P0 (0M) 2 or -PO (OM) 2 wherein M is H, alkali metal cation, alkaline earth metal cation, or organoammonium, ammonium, mixtures thereof and the like, with the proviso that when G in the above compound represented by the structure shown in formula (XII) is sulfonate, R ^ and R33 are not hydrogen. Illustrative and non-limiting examples of amine substituted organo acids of the formula (XII) to practice this invention include the alkali metal or ammonium salts of octylaminobismethylene phosphonic acid and dodecylaminobismethylene phosphonic acid. The substituted amino acids illustrative of the formula: they are useful herein as a component of group A, wherein the compounds of the formula (XIII) represent an extension of the amino acids, and wherein 34, 35/36 and R37 may be hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl, alkanol, polyalkoxy, alkenyl, sulfur-containing portions and phosphorus-containing portions. In addition, R34 and R35 can be covalently connected such as in cyclic amino acids such as proline. M is a symbol for a portion that is conveniently selected from hydrogen, alkali metal cation, ammonium or organoammonium, mixtures thereof and the like. The non-limiting and illustrative substituted acids of the formula: R38XR3gG (XIV) wherein R3g is selected from linear or branched, substituted or unsubstituted alkyl or alkenyl groups having 6 to about 20 carbon atoms and optionally containing one or more oxygen atoms, and X is absent or selected from a group consisting of -CH2- (methylene), oxygen, sulfur, -SS- and aryl, wherein aryl is substituted or unsubstituted phenyl, and R3g is absent or is selected from linear or branched alkylene or alkenylene groups, substituted or not substituted which contain 1 to 6 carbon atoms and optionally contain one or more oxygen atoms, and G is selected from -0S0 M, -S020M, 0P0 (0M) 2 or -PO (OM) 2, wherein M is H , alkali metal cation, alkaline earth metal or ammonium cation, with the proviso that: 1. when X is aryl and R35 is absent, G can not be S02OM, 2. when X is absent or methylene, G can not be PO (OM) 2, 3. When G is a phosphate, then R3g can not be substituted with phosphate, 4. When X is absent or is methylene or oxygen, G can not be phosphate, 5. when G is phosphate, R3g must be present and X can not be methylene and 6. when G is -S020Mg and X is absent or methylene, then R3g and R3g can not be alkyl or alkylene. (Mg = magnesium).

Illustrative and non-limiting examples of mercaptocarboxylic acids useful as a component of group A include, without limitation, those illustrated by the following schematic formula: 0 R40CHCOM | (XV) SH wherein R40 includes CI_3Q alkyl and C3_3C carboxyalkyl, M = H, alkali metal cations, alkaline earth metal cation, ammonium, organoammonium, mixtures thereof and the like. Illustrative and non-limiting components typical of group B include any of phosphates, phosphonates, phosphites and hypophosphites, borates, and mixtures thereof and the like. When employed in the compositions, method of use and methods of this invention, these phosphates, phosphonates, phosphites, hypophosphites, orthoborates, metaborates and pentaborates can have beneficial effects in lubrication at extreme pressures in metal working operations. The reduced forms of a component or components of group B may be useful as such and may also be oxidized in situ with air or other oxidizing agent. For example, phosphites can be oxidized to phosphates. Said beneficial effects are improved by the addition of these components to the organic compounds of group A described hereinabove.

The most preferred illustrative and non-limiting phosphates are orthophosphates such as the monobasic, dibasic or tribasic salt or mixtures thereof with a metal or alkali metals, preferably sodium or potassium or an ammonium or alkylammonium such as triethylammonium or triethanolammonium and Similar, and their complete or partial esters, although other similar phosphates may be employed if desired. In addition to the orthophosphates, the following phosphates can be used illustratively, like their salts: pyrophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphoserine, mixtures thereof and the like. Some or most of the phosphonates useful herein are illustrative of those compounds that can be conveniently represented by the formula: R25 (P0 (0R2g) 2) n (IX) wherein n in the above formula (IX) is an integer that varies independently from 1 to about 5, and R25 in the formula (IX) can independently be an organic portion or portions and a phosphonoorganic portion or portions, or portions containing organic amines or mixtures thereof and the like, and R2g is independently one or more of hydrogen or an organic portion or moieties, including alkyl, aryl, polyalkylene glycols, polyethylene glycols, polypropylene glycols, mixtures thereof and the like.

Suitable non-limiting and illustrative examples of acceptable phonates which are useful herein include 1-hydroxyethylidene-1, 1-diphonic acid, amino-trimethylene phonic acid, dodecylamino-bismethylene-phonic acid, which can be made by reacting dodecylamine, formaldehyde, phoric acid, and sodium chloride. hydrogen, hexamethylenediaminetetramethylenephonic acid, diethylenetriamine-pentamethylenephonic acid, N-phonomethylglycine, 2-phono-1,2,4-butanedicarboxylic acid, hydroxyphonoacetic acid, a salt or salts thereof, mixtures thereof and the like. To prepare the compositions of this invention (for example metalworking compositions), the amount of a component selected from group A, for example, is generally in the range from about 0.1% to about 75% or more, by weight of the total composition and most preferably on the scale of about 0.25% to about 25% by weight or more for the total composition (although one skilled in the art will recognize upon reading this description that greater or lesser amounts or concentrations may be used if desired to achieve the desired beneficial lubricating effect). For example, when a component of group A is used and a component of group B is used, the amount of the component of group B used is for example on the scale of about 0.1 to about 60%, and is preferably on the scale of about 0.25 to about 15% by weight (although greater or lesser amounts may be employed as recognized by an expert after reading this description including the examples). In other embodiments, a metal working method is provided comprising contacting the surface of the metal being worked or the surface of the tool with an aqueous solution of a fluid lubricating composition comprising a composition of this invention as described. at the moment. If desired, more than one component of group A and / or group B may optionally be used depending on the specific application, or in addition, if desired, one component of group A may be an adduct of components of group A and group B, whereby that resulting adduct component imparting an improved lubricant property contains a carboxylate portion and a portion of phorus within the same molecule. See table 1. When the group A component is exclusively used, the amount of said component employed is an effective lubricant amount, typically in the range of about 0.1 to about 75% or most preferably in the range of about 0.25% to about 25%, although higher or lower amounts may be employed as determined by those skilled in the art as an effective amount after reading this description.

The phonates illustrated above can be used as a component of group A to achieve one or more of the objects of this invention. When a phonate is employed, the concentration thereof is preferably in the range of about 0.1% to about 75% or most preferably in the range of about 0.10% to about 15% and more preferably in the range of about 0.10% a about 10% by weight, although higher or lower amounts can be used. This invention also comprises a method of feeding a water-soluble lubricating composition for working metals into a metal which needs and is a recipient thereof (capable of being worked), which comprises preparing an aqueous solution of a water-soluble lubricating composition for working metals by optional dilution of a composition of an aqueous solution of a fluid lubricating composition comprising one or more water soluble components selected from a first group (A) comprising: amides; polyamides; polyamino acids, salts and esters; polycarboxylic acids, salts or their esters; amino acids, salts and esters; sulfonic acids and salts; a sulfur compound selected from mercaptan, sulfur, disulfide and polysulfide; mercaptocarboxylic acids; susituated amino acids; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more portions selected from the group consists of carboxylate, sulfate, sulfonate, phosphate and phosphonate, present as free acids, or their salts; organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate and phosphonate, present as the free acids or their salts, and additionally a portion selected from sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester , amide, amine, ether, sulfide, disulfide or aryl; and optionally one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites and hypophosphites; preferably the balance is water, and the water-soluble composition is fed to the working portion of a metal by spraying or submerging in said water-soluble metalworking composition. Illustratively, by the use of this invention a lubricated metal surface is provided wherein said surface of said metal being worked and / or the surface of the tool are lubricated with a composition of this invention. By way of illustration, said lubrication originates by any convenient means such as immersion, humidification and otherwise similarly providing or feeding in some acceptable way a composition of this invention to the surface of the metal being worked in such a way that is used to produce a metal workpiece also in accordance with this invention.

The temperature at which the composition of this invention can typically be applied is preferably a suitable temperature, for example, such as could be achieved by those skilled in the art and illustratively, but not by way of limitation, may be on the scale of about 0 ° C to about 100 ° C or more or less, as measured in the fluid. Those skilled in the art will recognize that the temperature in the working zone of metal and the tool and the metal being worked will necessarily have to become significantly hotter during the work of the metal. If desired, a metal can be worked with a tool using a composition of this invention by first cleaning the metal and then practicing this invention on the metal. Those skilled in the art will recognize that various water-soluble additives may be employed in the compositions of this invention to improve or contribute to the properties that make possible broader functions with respect to the use of the compositions in metal working applications. The types of additives that are readily apparent to those skilled in the art include simple film forming lubricants and / or boundary lubricants, corrosion inhibitors, oxidation inhibitors, detergents and dispersants, viscosity index improvers, emulsion modifiers, anti-wear and anti-friction agents and foam depressants.

For example, additives may be employed to improve the boundary lubrication such as wear inhibitors, lubricity agents, friction modifiers and the like. Typical examples of such additives are metal dialkyldithiophosphates, metal diaryldithiophosphates, alkyl phosphates, tricresyl phosphate, 2-alkyl-4-mercapto-1,3,4-thiadiazole, metal dialkyl-dithiocarbamates, metal dialkyl phosphorodithioates, wherein the metal is typically zinc, molybdenum, tungsten or other metals, phosphors and olefins, sulphurated fats and olefins and paraffins, fatty acids, polyalkoxylated fatty acids, alkylene oxides, polyethylene oxides, polypropylene oxides, carboxylic acids and their salts, acid esters fatty acids including hydrolyzed castor oil; organic molybdenum compounds, molybdenum disulfide, graphite and borate dispersions. Such boundary lubricating additives are well known in the art. Other additives include detergents and dispersants that provide cleaning functions. Although the fluid compositions of this invention function as corrosion inhibitors at a certain pH scale, corrosion inhibitors that will function on a pH scale in which another ingredient may not function as a corrosion inhibitor may be employed in the compositions of this invention. Suitable examples of corrosion inhibitors include polyamino acids and phosphonates such as C? 2H25 (CH2P03H) 2. Typical examples of corrosion inhibitors known in the art are benzotriazole, tolyltriazole, other functionalized benzotriazoles, zinc chromiate, dithiophosphates such as zinc dithiophosphate, metal sulphonates in which the metal is an alkali metal, alkanolamines such as monoethanolamine and triethanolamine and substituted alkanolamines in which the base structure of the alkyl group is substituted to provide various properties, alkylamines such as hexylamine and trioctylamine, borate compounds such as sodium or potassium tetraborate or potassium pentaborate, and mixtures of borates with amines, carboxylic acids including polyaspartic acid at high pH (about 10 and more) and alkylaminocarboxylic acids particularly useful in hard water, sodium molybdate, boric acid esters such as monobenzyl borate and boric acid with various ethanolamines (which also act as a biostat), caprylic acid, nonanoic acid, Benzoic acid, nitro benzoic acid derivatives, alpha, omega-diacids such as sebacic acid, ammonium benzoate, mucic acid, hydroxybenzoic acid, sodium benzoate and triethanolamine salts of carboxylic acids with a carboxymethylthio group such as the triethanolamine salt of 1-1- (carboxymethylthio) undecanoic acid . Other corrosion inhibitors include 1-methylimidazole, 1- (3-aminopropyl) imidazole, 1,2-dimethylimidazole, mixtures thereof and the like, amines and substituted amines such as 2,2'-ethylenedioxy-bis (ethylamine), tris (2-aminoethyl) amine, N, N, N ', N' -tetrakis (2-hydroxyethyl) -ethylenediamine, and longer chain mono-, di-, and triamines such as 4- (aminomethyl) -1,8-octanediamine, iminobispropylamine, bishexamethylenetriamine, trioctylamine and polyethylenimine, mixtures thereof and the like. An additional class of inhibitors are biological pH regulators such as 3- [N, N-bis (2-hydroxyethyl (amino] -2-hydroxy-propanesulfonic acid. In addition, basic amino acids such as lysine and ornithine can also be added to provide inhibition. of corrosion, lysine and ornithine are non-toxic and are easily biodegradable and absorbed by the environment A more careful review of corrosion inhibitors is provided by Aruna Bahadur in a publication entitled "Chromate Substitutes For Corrosion Inhibitors in Cooling Water Systems" appearing n Corrosion Reviews, 11 (1-2), pp. 105-122, 1993, which is hereby incorporated herein by reference in its entirety.These fluids may be employed in processes for working metals for both ferrous and non-ferrous metals if The tests with non-ferrous metals such as brass, copper, aluminum and titanium indicate that the workpiece remains relatively free of deposits Discoloration It has been observed that the aqueous solutions of the polyaspartic acid salts are corrosion inhibitors for ferrous metals, as indicated by the US patent. 4,971,724 to Kalota et al. Therefore, metals, particularly ferrous metals, are free from harmful deposits and are in fact substantially protected from corrosion by the metalworking fluids of this invention. The water-based metalworking fluid compositions of this invention are particularly advantageous since there is little or no odor associated with their solutions in water. In addition, it has been observed that these fluids do not create a mist around the working area of the tool as is common with fluids containing water-based oil. Thanks to the lack of fog formation the work area remains virtually free of the floating fluid that leaves the machinery and the worker is substantially free of contamination by the fluid to work metals. The cost advantages of such fluid are obvious in alleviating environmental concerns, resulting in alternative disposal means. The metalworking fluids of this invention are useful in the different metalworking applications, such as those mentioned above, with any number of types of metals. In particular, they are useful for working ferrous metals such as iron, steel (carbon steel and low alloy carbon steel), stainless steel and nickel-based alloys. The non-ferrous metals that can be worked with the fluids of this invention are copper, brass, aluminum, magnesium, zirconium and titanium. In addition, alloys or mixed bodies made from materials such as cemented tungsten carbide in cobalt or nickel they can also be worked or formed using the components of this invention. C ?2H25N (CH2P03H) 2 (dodecylamino-bismethylenephosphonic acid) can be conveniently used when working aluminum metal as a component of group B. Polyalkylene oxide derivatives of fatty acids such as ricinoleic acid can also be used. Said metals are worked safely providing lubricity by means of the water-based fluids of this invention. A particularly important function of a metal working fluid of this invention in cutting operations is the cooling function to maintain a lower tool temperature, as well as the working temperature. This control helps minimize tool wear and distortion of the workpiece. Another function of the metalworking fluid of this invention is lubrication that can reduce friction such as occurs between the tool and the fragments produced during the cutting operation, as well as the reduction of friction between the tool and the workpiece. . In cutting operations of various types fragments of small pieces of metal are advantageously produced which are advantageously removed from the workpiece as soon as possible so that they do not jam the cutting tool. As used herein, the term "water-soluble" also includes, but is not limited to, the condition in which a substance forms a homogeneous transparent solution in water. Useful components in the compositions of this invention include those in which the group A component alone or a combination of a group A component and a component of group B are water soluble. As used herein, the term "metal work" is not limiting but includes illustratively and without limitation, procedures such as cutting, abrasion and forming, similar and over procedures. MC Shaw, According to "Principles of abrasive Processing", Clarendon Press, Oxford, 1996, which is incorporated herein in its entirety as a reference and who describes some aspects of metal work, the field of abrasion is It divides into two regimes, "rough removal abrasion" and "shape and finish abrasion". The first regime includes procedures in which the main objective is to remove unwanted material regardless of the quality of the resulting surface. The second regime includes operations in which form and finishing are the main concern and the wheels have to be periodically renewed to provide sharp cutting edges that are relatively free of adherent metals and flat areas by wear. This invention relates to all types of abrasion and formation. Illustratively, some of the abrasion types are rough abrasion, precision abrasion, surface abrasion, cylindrical abrasion, Decentral abrasion, internal abrasion, abrasion of feeding and abrasion of tool and the like. Some of the metal removal or metal cutting operations include, without limitation, turning, milling, grinding, drilling, sawing, reaming, widening, internal threading, brushing, drilling, external resizing and the like. Illustrative and non-limiting types of operations are presented in M. C. Shaw, "Metal Cutting Principles," Clarendon Press, Oxford, 1984, which is hereby incorporated in its entirety by way of reference. The metal removal procedures are considered a type of formation but involve the formation by removal of the metal. The training procedures typically have to do with the configuration of the metal without its removal. Some illustrative and non-limiting examples are coining, explosion tube forming, consolidation, roll forming, bar forging, tube rolling, bending, stamping and drawing among others. Such procedures typically require high pressures that are believed to induce plasticity at the metal at the "work" point and that are accompanied by increased temperatures. If wishing to be limited by theory, it is believed that the extreme pressure portion of the gasket chemically reacts with the metal surface during a pretreatment of the surface or during the working operation of the metal. In the same way, it is also believed that the Lubrication occurs through the removal of the chemically reacted film by contact. It is also believed that the film is regenerated by an additional reaction. The technical reference J. P. Byers, "Metalworking Fluids", Marcel Decker, Inc., NY, 1994 reports on this point and is incorporated herein in its entirety as a reference. Also as used herein, the term "metal work" encompasses, but is not limited to, a process or procedures that utilize a tool that performs the work of the metal in a part and / or a part itself that is being worked. and to receive the actions of a tool. As used herein, the term "polycarboxylic" includes carboxylic acids or salts or esters thereof containing two or more carboxylate moieties. As used herein, the added functional effects, include but are not limited to, the lubricating effect at combined extreme pressures of the components of group A and group B that was greater than that obtained using each component separately. Those skilled in the art will recognize that cations such as sodium, potassium, ammonium and organoammonium and the like are employed in the compositions and methods of this invention (with various components of group A and group B) as counterions of an anion, the latter being capable of he responsible in some way for the improved property without being limited by theory. (Such as lubrication). This invention also comprises a method for working metals, which comprises providing as a lubricant to said metal, an effective lubricating amount of a fluid lubricating composition comprising one or more water-soluble components selected from: a first group (A) which comprising: amides; polyamides; polyamino acids, salts and esters; monocarboxylic acids having one to six functionalized or non-functionalized carbon atoms, examples are: C 2 -C 2 -alkyl sulfone, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that this does not include -hydroxybutyric acid and 3-hydroxybutyric acid; with the proviso that these acids are not 2-hydroxybutyric acid or 3-hydroxybutyric acid; polycarboxylic acids, salts or their esters; amino acids, salts and esters; sulfonic acids and salts; a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide; mercaptocarboxylic acids, salts and esters; keto acids; organo-acids substituted with amine; amino acids substituted, salts and esters; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as free acids, or their salts; organic acids containing one or more portions selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids or their salts, and additionally a portion selected from the group consisting of sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester, amide, amine, ether , sulfur, disulfide or aryl; and optionally one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites and hypophosphites; composition that provides a synergistic lubricating effect or added functionality when used as a mixture of one or more components of group (A) and group (B). This invention also comprises feeding a water-soluble lubricating composition for working metals to a metal useful for receiving the same, optionally comprising diluting said water-soluble lubricating composition to work metals and feeding the water-soluble composition optionally diluted or undiluted to a portion of the metal, then applying said composition effectively to said metal. This invention also comprises a method for using a water-soluble metalworking lubricant composition, comprising providing as a lubricant to said metal, an effective lubricating amount of a fluid lubricating composition comprising one or more water-soluble components selected from: a first group (A) comprising: amides; polyamides; polyamino acids, salts and esters; acids monocarboxylics having one to six functionalized or non-functionalized carbon atoms, examples are: Cl- alkoxy- < - sulfone, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that this does not include 2-hydroxybutyric acid and 3-hydroxybutyric acid; polycarboxylic acids, salts or their esters; amino acids, salts and esters; sulfonic acids and salts; a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide; mercaptocarboxylic acids, salts and esters; keto acids; organo-acids substituted with amine; amino acids substituted, salts and esters; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as free acids, or their salts; organic acids containing one or more portions selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids or their salts, and additionally a portion selected from the group consisting of sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester, amide, amine, ether, sulfide, disulfide or aryl; and optionally one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites and hypophosphites; composition that provides a lubricating effect synergistic or added functionality when used with one or more components of group (A) and group (B). This invention also comprises a method for working metals, further characterized in that said method comprises providing as a lubricant to said metal, an effective lubricating amount of a lubricating composition comprising one or more water-soluble components selected from: a first group (A) comprising : amides; polyamides; polyamino acids, salts and esters; monocarboxylic acids having one to six functionalized or non-functionalized carbon atoms, examples are: I-C2Q alkoxy sulfone, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that this does not include the acid 2- hydroxybutyric and 3-hydroxybutyric acid; polycarboxylic acids, salts or their esters; amino acids, salts and esters; sulfonic acids and salts; a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide; mercaptocarboxylic acids, salts and esters; keto acids; organo-acids substituted with amine; amino acids substituted, salts and esters; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as free acids, or their salts; organic acids containing one or more portions selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids or their salts, and additionally a portion selected from the group consisting of sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester, amide, amine, ether, sulfide, disulfide or aryl; and optionally one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites and hypophosphites; composition that provides a synergistic lubricating effect or added functionality when used as a mixture of one or more components of group (A) and group (B). This invention also comprises a lubricated metal surface, wherein said surface of said metal being worked has been contacted with a composition comprising an effective amount of a fluid lubricating composition comprising one or more water-soluble components selected from: ** a first group (A) comprising: amides; polyamides; polyamino acids, salts and esters; monocarboxylic acids having one to six functionalized or non-functionalized carbon atoms, examples are: CI-C2Q sulphone alkoxy, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that this does not include the acid 2- hydroxybutyric acid and 3-hydroxybutyric acid; polycarboxylic acids, salts or their esters, amino acids, salts and esters, sulfonic acids and salts, a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide, mercaptocarboxylic acids, salts and esters; keto acids; organo-acids substituted with amine; amino acids substituted, salts and esters; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as free acids, or their salts; organic acids containing one or more portions selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids or their salts, and additionally a portion selected from the group consisting of sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester, amide, amine, ether, sulfide, disulfide or aryl; and optionally one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites and hypophosphites; composition that provides a synergistic lubricating effect or added functionality when used as a mixture of one or more components of group (A) and group (B). This invention also comprises a worked piece of metal or a piece being worked, said work being accomplished or having been achieved by having contacted or provided said metal with an effective amount of a fluid lubricating composition comprising one or more hydraulic components. Selected solvents of: ** a first group (A) comprising: amides; polyamides; polyamino acids, salts and esters; monocarboxylic acids having one to six atoms functionalized or non-functionalized carbon atoms, examples are: C 2 -C 2 alkoxy sulfone, alkylene phosphonates, sulfur, functionalized amines and the like, salts and esters, with the proviso that this does not include 2-hydroxybutyric acid and 3-hydroxybutyric acid; polycarboxylic acids, salts or their esters; amino acids, salts and esters; sulfonic acids and salts; a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide; mercaptocarboxylic acids, salts and esters; keto acids; organo-acids substituted with amine; amino acids substituted, salts and esters; organosulfonates; sodium or potassium sulfide, sodium or potassium hydrogensulfide, organic acids containing one or more selected portions of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as free acids, or their salts; organic acids containing one or more portions selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate or phosphonate, present as the free acids or their salts, and additionally a portion selected from the group consisting of sulfone, sulfonamide, sulphonic ester, sulfate ester, ketone, carboxylic ester, amide, amine, ether, sulfide, disulfide or aryl; and optionally one or more components selected from a second group (B) comprising: phosphates, borates, phosphonates, phosphites e-hypophosphites; composition that provides a synergistic lubricating effect or added functionality when used as a mixing one or more components of the group (A) and group (B) to produce said article of manufacture. One skilled in the art will know how to make and use the compositions described herein after receiving this description. In the composition of claim 1, the component of group A is a salt or mixture thereof, or the component of group B is a salt or mixture thereof, or both components of group A and group B are a salt or a mixture of the same or no component of group A or group B is a salt. 1, 3, 6-tricarboxylhexane is prepared by hydrolyzing tricianohexane with potassium hydroxide in water. Tricianohexane was obtained as a co-product from the electrohydrodimerization of acrylonitrile. To prepare a composition of this invention, one skilled in the art will typically add a component of group A optionally to a component of group B to form a mixture in a selected amount of water. There is no preferred order with respect to mixing or order of addition. The temperature at which a composition can be prepared can be at room temperature and at normal atmospheric pressure. The use of a water-soluble component or components is necessary. Those skilled in the art will recognize that an effective amount of a functional portion component (lubricant) of group A and optionally of group B are present in a composition of this invention to achieve objects of it. These can be provided in acid, ester, salt or a mixture of forms, such as an ionic form (such as a salt or salts). The amount provided is such that a functional lubricant effective amount is provided in a composition, method of use or article of manufacture prepared using the invention. By way of illustration but not limitation, an effective amount of lubricant is that amount of lubricant that adequately lubricates the surface of the metal being worked or tool that is working the metal, for example, and that achieves the objectives of a lubricant. quality as those that would be recognized by those skilled in the art. When a Group A component without a Group B component is employed, those skilled in the art will recognize that an aqueous solution containing an effective lubricant amount of the Group A component can be applied to the surface of the metal or tool being lubricated. This invention also comprises compositions in which a component of group B with a component of group A is used. In such situations an effective lubricating amount of a component of group B is used together with an effective amount of a component of group A. Components illustrated in the examples are commercially available, except when mentioned otherwise.

EXAMPLES EXAMPLE 1 A test of four extreme pressure balls was carried out in accordance with the procedure of ASTM D2783, "Standard Mech- ket for Measurement of Extreme-Pressure Porperties of Lubricanting Fluids (Four-Ball Method)" incorporated herein by way of reference in its entirety This test is used to qualify the relative load carrying properties of lubricating fluids under a constant set of conditions. In this test, a steel bar is rotated under load against three steel balls held stationary. The test lubricant covers the three lower balls. The load is increased on the rotating ball while the test progresses and the measurements of the diameter of marks on the balls are made for ten ascending loads below the welding point. The data are reported in table 1 below as wear index per load (kgf), average mark diameter (mm) and weld point (kgf). The wear index per load is calculated from the tabulation of the brand diameter versus the applied load. The corrected applied loads (which compensate for the Hertzian diameter) of the ten largest loads immediately preceding the point of welding are averaged. Since brand diameters are always measured at the same loads applied, the index becomes a function of the fluid and the metals. Since all the tests are carried out with the same type of metal, the wear index per load is used to classify the capacities of a series of lubricants to minimize wear. Table 1 is a set of data that has been generated by carrying out the two previous tests and which reports data for the extreme pressure test of four balls as average Hertz load, welding loads, non-collapsing load and brand diameter for the test of four extreme pressure balls, and the data is reported for the coefficient of friction. Note that the maximum load and torque values were generated as a result of the commissioning of the ASTM D2738 method. These data indicate that the compositions of this invention are highly useful in metal forming and metalworking operations. ASTM D3233B test, "Standard Test Methods for Measurement of Extreme Pressure Properties of Fluid Lubricants (Falex Pin and Vee Blok Methods)" incorporated herein by reference in its entirety, was carried out at a fluid temperature of 49 ° C at 290 rpm and a concentration by weight that provides 365 milliequivalents / L of the component shown below for most examples. The test component was generally dissolved in a container to provide 365 milliequivalents / liter in water, with and without phosphate at a level of approximately 0.75% or approximately 1.5% as orthophosphate, with water being the balance of the composition. These test materials were evaluated using ASTM D-2783 Extreme Pressure Four ball test and ASTM D3233B Pin and Vee block test. The kinds of components useful for practicing this invention for working metals are contained in the following Table 1. (Except when otherwise indicated, when a salt was used here, the potassium salt was used. 9.5 to 10). In the interpretation of the results of ASTM D-2783, a welding point of 250 to 400 kg-f is considered a high extreme pressure capacity with a value of 315 being an average for high extreme pressure fluids. The values of 500 kg-f and more are considered superior to the behavior of high extreme pressure normally found. The maximum load of the test is 800 kg-f.

N 4 L L L L • I heard 00 Lp vO OR OR -S9 - L EXAMPLE 2 A series of experiments was carried out using the methods of ASTM D2783 and ASTM 3233B to measure the extreme pressure lubricating properties of compositions selected from various classes of compounds. The p-H of the solutions was generally adjusted to about 10. The results are shown in figures 1 to 12. Figure 1 shows the counter-load-label diameter applied for sodium polyglutamate in the presence and absence of sodium orthophosphate. Figure 2 shows the counter-load mark diameter applied for polyasparagine in the presence and absence of potassium orthophosphate. Figure 3 shows the counter-load brand diameter applied for L-aspartic acid in the presence and absence of potassium orthophosphate. Figure 4 shows the anti-charge label diameter applied for L-asparagine in the presence and absence of potassium orthophosphate. Figure 5 shows the counter-load-label diameter applied for L-cystine in the presence and absence of potassium orthophosphate. Figure 6 shows the torque against load applied to L-cystine and L-cysteine in the presence and absence of potassium orthophosphate. Figure 7 shows the counter-charge mark diameter applied for dithiodipropionic acid in the presence and > absence of potassium ortsphosphate. Figure 8 shows the counter-load-label diameter applied for urea in the presence and absence of potassium orthophosphate. Figure 9 shows the Brand diameter against load applied to 1-hydroxyethylidene-1,1-diphosphonic acid in the presence and absence of potassium orthophosphate. Fig. 10 shows the counter charge diameter applied for 2-phosphono-1,2,4-butanetricarboxylic acid in the presence and absence of potassium orthophosphate. Figure 11 shows the counter charge diameter applied for sodium sulfide in the presence and absence of potassium orthophosphate. Figure 12 shows the counter-load-label diameter applied for 2-phosphono-1,2,4-butanedicarboxylic acid (PBTC) in the presence and absence of potassium orthophosphate. Figure 14 shows the counter-load label diameter applied for bovine serum albumin in the presence and absence of orthophosphate. Figure 15 shows the counter-load brand diameter applied for poly (2-ethyl-2-oxazoline) in the presence and absence of phosphate. Figure 16 shows the counter-charge mark diameter applied for malic acid in the presence and absence of phosphate. Figure 17 shows the counter-load brand diameter applied for tricarboxyhexane in the presence and absence of phosphate. Figure 18 shows the counter-load-label diameter applied for succinnamic acid in the presence and absence of phosphate.

EXAMPLE 3 Test solutions were prepared by dissolving 1,2,4,4-butacarboxylic acid in water and adjusting the pH to . The solutions were tested using a four-ball extreme pressure machine. The brand diameter and the applied load at which the welding occurred were measured. Figure 13 below shows the results of the four-ball extreme pressure test. The high pressure shows the independent lubricating properties of this molecule that can be used with or without a component of group B.

EXAMPLE 4 Bovine somatotropin (bST) is an animal protein that can be used in this invention as a component of group A, for example. The bST solution was tested by the method of ASTM D4172"Wear Preventative Characteristic of Lubricating Fluids (Four-ball test)" with aluminum and steel balls. No noise occurred during the tests for the three concentrations of bST shown in Table II below. The brand diameter and the coefficients of friction indicate that the fluid has a lubricating capacity.

TABLE II Figure 14 shows using the method of ASTM D2783 that a mixture of bST with phosphate produced a synergistic lubricant effect at extreme pressure producing a weld load of 200 kg with bST only, and a weld load of 620 when bST was used and phosphates EXAMPLE 5 A solution of bovine serum albumin (BSA) at 7.5% and phosphate (P04 ~ 3) to * 5.0% in water at pH 8.6 was diluted to a ratio of 9: 1 with water and run in the tester. Timken using a steel ring and a carbon steel block, obtaining a coefficient of friction of 0.20.

(Conditions: normal applied force of .908 kg). The source of the bovine serum albumin used was the fraction V material, isolated by the heat shock method (material obtained from Sigma Chemical Company). BSA solutions in water were tested in the four-ball tester, using three fixed aluminum balls and a rotating steel ball. A solution of 7.5% BSA produced a brand diameter of 0.7 mm, producing no noise during the test. A solution of BSA at 0.75% produced a brand diameter of 0.6 mm, neither making any noise during the test. Using the method of ASTM D2783, it was shown that a mixture of BSA with phosphate produced a synergistic lubricating effect at extreme pressure, producing a 250 kg welding load without phosphate, and a welding load of 620 kg when phosphate was added.

EXAMPLE 6 A solution of dodecylamino-N, N-bismethylenephosphonic acid at 1% by weight in water, adjusted to a pH of about 6, was examined using the test method described in ASTM.

D4172, "Wear Preventative Characteristic of Lubricating Fluids (Four-Ball test) ", incorporated herein by reference, using aluminum and steel balls.The mark diameter on steel was 0.45 mm, and on aluminum was 0.55 mm in both cases (see Table III below) , and there was no noise some (sound of the test itself) during the test. These results indicate that the fluid has a lubricating capacity. This is an example of a component of group A that is being used exclusively, that is, without a component of group B in putting this invention into practice.

EXAMPLE 7 A solution of octylsulfonylbutyric acid at 1% by weight in water, adjusted to a pH of about 9, was examined using the test method described in ASTM.

D4172, "Wear Preventative Characteristic of Lubricating Fluids (Four-Ball test) ", incorporated herein by reference, using 6061 aluminum balls. The mark diameter on aluminum was 0.49 mm (see Table III below), and no noise occurred during the test. it was further examined using a method involving 51.43 cm hole drilling in an aluminum block 356. No noise was produced in the drilling process, and no oversized hole was found.These results indicate that the fluid has a lubricating capacity. This is an example of a component of group A that is being used exclusively, that is, without a component of group B when putting this invention into practice.

TABLE III EXAMPLES OF GROUP A THAT ARE USED EXCLUSIVELY NT = Not put to pmeba Without being limited, this invention encompasses several compositions, uses and effective use options depending on the composition and the intended use., as is evident after reading this specification, and is not limited to any specific operation, composition or use but, for example, includes those operations by means of which a composition is applied to, applied by, put in contact with, or provided effectively, by any means of effective application including, illustratively, those known to those skilled in the art and including, for example, flooding, pumping, fogging, spraying and the like, to a metal or a tool depending on , in fact, of use and composition. All parts and percentages used herein are by weight, unless otherwise specified. Although the invention has been described above in terms of some specific embodiments which are described in considerable detail, it should be understood that this description is only by way of example, and that the invention is not necessarily limited thereto, since modalities and techniques of Alternative operations will become apparent to those skilled in the art in view of this description. Accordingly, modifications that can be made without departing from the spirit of the invention described above are contemplated.

Claims (96)

1. NOVELTY OF THE INVENTION CLAIMS 1. A composition for working metals, characterized in that it comprises a functionally effective lubrication amount of a fluid lubricating composition comprising one or more water-soluble components selected from: (a) a first group (A) comprising: amides, with the proviso that that when said amides are represented by the formula: R7CONR8R9 (V) wherein R7, Rβ and R9 are independently hydrogen, alkyl, functionalized alkyl, aryl, functionalized aryl, a functional group containing alkyl or aryl groups, NH2, NHRIQ ° NR11R12 wherein R ## R1X and RX2 are independently hydrogen, alkyl, functionalized alkyl, aryl or functionalized aryl groups, which Rg and R9 may not be polyethylene imine; then R7 is MOOC (CH2) 8 ~ »R8 and R9 may not be hydroxyalkyl of C? -4, which when R7 is C? 2- alkyl? 8 # R8 R9 May not be hydroxyethyl, if one of R? and R9 is hydrogen, and the other is C3- alkyl, then R7 may not be selected from -CH2CH2COOH, -CH = CHC00H or orthocarboxyphenyl, and when one of R3 or R9 is H, and the other is CH2 H2CH2CH (- NH2) COOH, then R7 may not be an alkyl group containing from 8 to 22 carbon atoms; polyamides; amino acids and salts or esters thereof; polyamino acids and salts or esters thereof; carboxylic acids and salts or esters thereof, wherein said carboxylic acids are mono- or polycarboxylic acids, with the conditions (1) that when said monocarboxylic acids have from 1 to 6 carbon atoms optionally functionalized with a functional group selected from ? -C20 sulfone alkoxy, alkylene phosphonates, sulfides or functionalized amines, and salts or esters thereof, then said monocarboxylic acid does not include 2-hydroxybutyric acid and 3-hydroxybutyric acid; and (2) that when said carboxylic acid is represented by the formula: R? C02H (I) wherein in relation to formula (I), Rx is hydrogen, alkyl of C? _g or Rx is RaORj -, -, in where Ra is linear or branched alkyl of Cg_20 and Rb is linear or branched alkylene of C? _ g, or Rx is RCSR? -, where Rc is C? _20 alkyl? And Rd is alkylene or hydroxyalkylene of C? _g , Rx can not be alkyl substituted with 3-carboxypropyl or 2-carboxymethyl; keto acids and salts or esters thereof; organic acids substituted with amine or salts thereof, with the proviso that when said organic acid substituted with amine, or a salt thereof is of the formula: R3? N (R33) R32G (XII) wherein R3X is selected from hydrogen or linear or branched or substituted or unsubstituted alkyl, alkenyl or alkoxy groups, having from 6 to 20 carbon atoms, optionally containing one or more oxygen atoms, R32 is absent or selected from hydrogen or linear or branched or substituted or unsubstituted alkylene or alkenylene, alkoxy or alkylamino groups, containing from 1 to 6 carbon atoms, optionally containing 1 or more oxygen atoms, R33 is selected from hydrogen or linear or branched, substituted or unsubstituted alkyl or alkenyl groups having from 6 to 20 carbon atoms, optionally containing one or more oxygen atoms, and G is selected from -CO2-M , -OSO3M, -S02OM, -OPO (OM) 2 or -PO (OM) 2, wherein M is H, alkali metal cation, alkaline earth metal or ammonium cation, when G is sulfonate, then R3X and R33 are not hydrogen; sulfonic acids and salts thereof, sulfonates; a sulfur compound selected from mercaptan, sulfur, disulfide or polysulfide; mercaptocarboxylic acids and salts or esters thereof; substituted amino acids and salts or esters thereof; organosulfonates; Sodium or potassium sulfide, Sodium hydrogen sulphide or Potassium hydrogen sulfide; organic acids containing one or more portions selected from the group consisting of carboxylate, sulfate, sulfonate, phosphate and phosphonate, present as free acids or salts thereof optionally containing a selected portion of sulfone, sulfonamide, sulphonic ester, sulfate ester, carboxy, keto, amide, amine, ether, sulfide, disulfide or aryl ester; borates; proteins; substituted acids, with the proviso that when said substituted acid is of the formula: R3ßXR39G (? IV> wherein R38 is selected from linear or branched, substituted or unsubstituted alkyl or alkenyl groups, having from 6 to 20 carbon atoms, optionally containing one or more oxygen atoms, X is absent or selected of the group consisting of -CH2-, oxygen, sulfur, -SS- and aryl, wherein aryl is substituted or unsubstituted phenyl, R39 is absent or is selected from linear or branched, substituted or unsubstituted alkylene or alkenylene groups containing from 1 to 6 carbon atoms, optionally one or more oxygen atoms, or (CH2CH2-O) n, wherein n is from 1 to 10, and G is selected from OSO3M, -SO2O, -OPO (OM) 2 or -PO (O) 2, wherein M is H, alkali metal cation, alkaline earth metal cation, or ammonium, so that: 1) when X is aryl and R35 is absent, G can not be SO2OM, 2) when X is absent or methylene, G can not be P0 (0M) 2 3) when G is phosphate, then R38 can not be substituted with phosphate, 4) X is absent or is methylene or oxygen, G can not be phosphate, 5) when G is phosphate, R39 must be present and X can not be methylene, 6) when G is -S? 2? Mg, and X is absent or is methylene, then R38 and R39 can not be alkyl or alkylene; and optionally (b) one or more selected components of a second group (B) comprising phosphates, borates, phosphonates, phosphites and hypophosphites. 2. - The composition according to claim 1, further characterized in that said composition it further comprises reaction products of said composition associated with a component or components therein, or the application of said composition to a metal being worked or tool that works the metal, or both. 3. The composition according to claim 1, further characterized in that said fluid lubricating composition has a lubricating property selected from the group consisting of extreme pressure, boundary lubricant, single or antiwear film, or a combination thereof. 4. The composition according to claim 1 or 3, further characterized in that said fluid lubricating composition is an extreme pressure lubricant, and said component of the group (A) is a monocarboxylic acid having from 1 to 6 carbon atoms. optionally functionalized with a functional group selected from α-C 20 sulfone alkoxy, alkylene phosphonates, sulfides or functionalized amines, and salts or esters thereof. 5. The composition according to claim 1 or 3, further characterized in that said fluid lubricating composition is a boundary lubricant, and said component of group (A) has the chemical structure R? COOH, where; Rx is Ra0Rb ° RcSRd 'wherein Ra is linear or branched alkyl of Cß-20' Rb is linear alkylene or branched from C? _g, Rc is C? _20 alkyl? 'and Rd is alkylene or hydroxyalkylene of C? _g. 6. The composition according to claim 1, further characterized in that said polycarboxylic acid comprises a polymer with repeating units containing carboxylate groups. 7. The composition according to claim 1 or 3, further characterized in that said component of the group (A) is an amide or a polyamide in which said polyamide is a molecule that contains 2 or more amide groups, or a polymer in which the repeating unit contains an amide group. 8. The composition according to claim 7, further characterized in that said polyamide is a polymer with repeating units containing amide groups, or wherein said amide or polyamide is a water-soluble amide or water-soluble polyamide, respectively. 9. The composition according to claim 7, further characterized in that said amide is a compound or its salt, and wherein the nitrogen can be substituted or unsubstituted, and which is represented by the formula: R7C0NR8R9 (V) 10. The composition according to claim 7, further characterized in that said amide is O R or II I -C - N- (CH2) n-COOM wherein n is an integer that independently varies from 2 to 10, and R42 is hydrogen or alkyl of Cx to C20- 11. The composition according to claim 7, further characterized in that said amide is selected from the group consisting of asparagine. , maleamic acid, urea, biuret, polyasparagine, glutamine, polyurea, N, N-dimethyloethamide, oleoamide, guanidine, pyroglutamic acid, polyacrylamide, poly (2-ethyl-2-oxazoline), salts thereof and mixtures thereof. 12. - The composition according to claim 11, further characterized in that said amide is selected from the group consisting of asparagine, maleamic acid, urea, polyasparagine, glutamine, pyroglutamic acid, polyacrylamide, poly (2-ethyl-2-oxazoline) , or salts thereof and mixtures thereof. 13. The composition according to claim 1, further characterized in that said component of group (A) is a carboxylic acid or its salt, represented by the formulas: R? C02H (I) and 2 (H?) MCHC02H] n (CHy) or R3 (II) wherein in relation to formula (II) ', R2 and R3 are the same or different independently, and may be independently hydrogen or oxygen or an organic group including alkyl, and / or aryl, mercapto, thio or dithiorgan portions, hydroxy, hydroxyalkyl, alkenyl, or alkoxy, alkoxyalkyl or aromatic portions when used in this formula (II), x and y are numerically 1 or 2, m is from 0 to about 40, or is from 0 to about 18, and n is from 1 to about 5000 or 7000 or more, and m, n, i are independent integers, with the proviso that Rx can not be alkyl substituted with 3-carboxypropyl or 2-carboxymethyl. 14. The composition according to claim 13, further characterized in that said carboxylic acid is selected from the group consisting of n-phosphonomethylglycine, and water-soluble salts and esters; lactic acid, formic acid, glycolic acid, glyoxylic acid, glyceric acid, octylthiobutyric acid, octylthiopropanoic acid, octyloxypropanoic acid, decyloxypropanoic acid, dodecyloxypropanoic acid, 4-methylthio-2-hydroxy-butyric acid, and salts and esters thereof and mixtures thereof. 15. The composition according to claim 14, further characterized in that said carboxylic acid is selected from the group consisting of N-phosphonomethylglycine and its salts and water-soluble esters, formic acid and its salts and esters, lactic acid and its salts and esters , and mixtures thereof. 16. The composition according to claim 1, further characterized in that said carboxylic acid is a polycarboxylic acid selected from the group consisting of polyacrylic acid, butacarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, undecanedioic acid, propanedicarboxylic acid, tartaric acid, sebacic acid, maleic acid, fumaric acid, citric acid, itaconic acid, citraconic acid, malic acid, aconitic acid and brazilic acid and tricarboxyhexanes, and salts and esters of the same. 17. The composition according to claim 16, further characterized in that said polycarboxylic acid is selected from the group consisting of polyacrylic acid, butantetracarboxylic acid, oxalic acid, succinic acid, tartaric acid, citric acid and tricarboxyhexanes, and salts and esters of the same. 18. The composition according to claim 17, further characterized in that said polycarboxylic acid is 1, 3, 6-tricarboxihexane or a salt thereof, or 1,2, 3, 4-butantetracarboxílico acid, or a salt thereof. 19. The composition according to claim 1 / further characterized in that said component of group (A) is an amino acid or a salt thereof. 20. - The composition according to claim 19, further characterized in that said amino acid is selected from amino acids that include both the naturally occurring amino acids and the manufactured compounds which contain at least one carboxylic acid group and one amine group and are represented by the formulas: R4 (CHNH2C02H) r O (III) R5 [(CHx) m (CHNH2C02H)] or (CHy) pRg O (IV) R5 [(CHX) m (CHNH2 (CH2) 2C02H) nl or <; y) pR6 (IVA) wherein R4, R5 and Rg in the formulas (III) and (IV) are independently hydrogen, alkyl or aryl, carboxyl, carboxymethyl, hydroxyalkyl or amine, x, y and z as used in these formulas, are the same or different independently, and 1 or 2, m and p as used in these formulas, are the same or different independently, and can be from 0 to 6, and r is an integer that varies independently from 1 to 10 and provided that, nonetheless , nyo must be at least 1, but they can be whole from 1 to 6 independently, salts or esters of the same. 21. The composition according to claim 20, further characterized in that the component of the group (A) is selected from hydroxymethanine analog, polyamino acid, a homopolymer of an amino acid, or a random or block copolymer of an individual amino acid or two or more amino acids or salts thereof. 22. - The composition according to claim 1, further characterized in that said component of the group (A) is a polyamino acid, or salts thereof. 23. The composition according to claim 22, further characterized in that said polyamino acid is selected from polyaspartic acid and its salts, and polyglutamic acid and its salts, and mixtures thereof. 24. The composition according to claim 22, further characterized in that said polyaminoacid is prepared by synthesis, or is obtained from natural sources of protein, both of natural origin and of vegetable origin, which are water-soluble as the free polymer or as a salt, and as described by the following formula: H [NH (CR23R24) mc °] nOH (VIII) wherein m, as used in the formula (VIII), is an integer that varies independently from 1 to 12, n is an integer that varies independently from 2 to about 2000 or more, and is selected so that the amino acid remains water-soluble, R23 and R24 / as used in the formula (VIII), can be the same or different independently, and vary within a polymer chain and independently consist of hydrogen or C02H2, --CH2C02H, -CH2CH2-C02H, -CH3, -CH2CH3, -CH2CH2CH3, CH2CH2CH2CH3, CH (CH3) 2, -CH2CH (CH3) 2, - (CH2 ) 0X 'where o = 0 to 20 and X can be R23, -OH, -SH , -SSCH2CH (NH2), - CO2H, -SCH3, phenyl, tolyl, hydroxyphenyl, guanidinyl, pyrrolidinyl, NH2, imidazoyl, indolyl and acetoamide, and mixtures thereof. 25. The composition according to claim 22, further characterized in that said polyamino acid component is polyproline or a proline copolymer with another amino acid or a salt thereof or an acidic, basic or neutral amino acid, or a salt thereof, or a mixture of it. 26. The composition according to claim 19, further characterized in that said acid amino acid is selected from the group consisting of aspartic acid and glutamic acid, and isomers and racemic forms thereof, and N, N-di (2-) acid. carboxymethyl) N-methylphosphonic, N-phosphonomethylglycine, salts, derivatives and esters thereof, O-phosphoserine, and mixtures thereof. 27. The composition according to claim 19, further characterized in that said basic amino acid is selected from the group consisting of arginine, histidine, ornithine, tryptophan, and mixtures thereof. 28. The composition according to claim 19, further characterized in that said amino acid is a sulfur-containing amino acid. 29. The composition according to claim 28, further characterized in that said sulfur-containing amino acid is selected from the group consisting of cysteine, cystine, hydroxymethionine analog, homocysteine, felinin, penicillamine, methionine, isovaltin, vitamin U, a salt thereof, and mixtures thereof. 30. The composition according to claim 19, further characterized in that said amino acid is selected from alanine, tyrosine, asparagine, valine, glutamine, glycine, hydroxyproline, isoleucine, leucine, phenylalanine, serine, threonine, thyroxine, norleucine or norvaline. 31. The composition according to claim 1, further characterized in that said component of the group (A) is an organosulfonate. 32. The composition according to claim 31, further characterized in that said organosulfonate is represented by the formula: © (vp) wherein R22 in formula (VII) is independently alkyl, alkoxy, hydrogen, aryl, aminoalkyl, amine, carboxyl, hydroxyl or amide, and M is independently hydrogen, alkali metal, ammonium, organoammonium, or mixtures thereof. 33. - The composition according to claim 32, further characterized in that said organosulfonate has an alkyl group that is substituted. 34. - The composition according to claim 31, further characterized in that said organosulfonate is selected from the group consisting of 4-octylbenzenesulfonic acid, 2-octylbenzenesulfonic acid, 3-octylbenzenesulfonic acid, 4-nonylbenzenesulfonic acid, 2-nonylbenzenesulfonic acid, 3-nonylbenzenesulfonic acid, 4-decylbenzenesulfonic acid, 2-decylbenzenesulfonic acid, 3-decylbenzenesulfonic acid, 4-undecylbenzenesulfonic acid, 2-undecylbenzenesulfonic acid , 3-undecylbenzenesulfonic acid, 4-dodecylbenzenesulfonic acid, 2-dodecylbenzenesulfonic acid, 3-dodecylbenzenesulfonic acid, and salts thereof. The composition according to claim 31, further characterized in that the organosulfonate is present as the alkali metal, ammonium or organoammonium salt, or a mixture thereof. 36.- The composition according to claim 1, further characterized in that the phosphonates of group (A) or group (B) are selected from the group consisting of those represented by the formula: R25 (PO (OR2g) 2) n (IX >; wherein n is an integer from 1 to about 5, R25 is independently an organic portion, phosphonoorganic portions, organic portion containing amine or mixtures thereof, and R2 is independently hydrogen or an organic portion including alkyl, aryl, polyalkylene glycols, polypropylene glycols, mixtures thereof, and the like. 37.- The composition according to claim 36, further characterized in that said phosphonate is selected from (1-hydroxyethylidene, 1-diphosphonic acid, aminotri (methylene phosphonic) acid, dodecyl-aminobismethylene phosphonic acid, (hexamethylene-diamino-tetra) acid (methylene phosphonic), diethylene triamine penta (methylene phosphonic acid), N-phosphonomethylglycine acid, 2-phosphono-1,2,4-butanetricarboxylic acid, hydroxyphosphonoacetic acid, and salts thereof or mixtures thereof. according to claim 1, further characterized in that the component of group A is a sulfonacid of the formula: R27S02R28G (X) wherein R27 is selected from linear or branched, substituted or unsubstituted alkyl, alkenyl, alkoxy or alkylamino groups, which have from 6 to 20 carbon atoms, optionally containing one or more oxygen atoms, R28 is absent or is selected from alkylene or alkenylene, alkoxy or alkylamino groups linear or branched, substituted or unsubstituted, containing 1 to 6 carbon atoms, optionally containing 1 or more oxygen atoms, and G is selected from CO2M, 0S03M, SO2OM, OPO (OM) 2 or P0 (0M) 2, where M is H, alkali metal cation, alkaline earth metal cation, ammonium, and mixtures thereof. 39.- The composition according to claim 38, further characterized in that the sulfonacid is selected from octylsulfonylbutyric acid, octylsulfonylpropanoic acid, dodecylsufonylbutyric acid, dodecylsulphonylpropanoic acid, N-octylsulfonyl-beta-alanine, nonilaminosulfonylpropanoic acid, salts thereof or mixtures thereof. the same. 40.- The composition according to claim 1, further characterized in that the component of group (A) is a keto acid of the formula: R29 (C = O) R30G (XI) wherein R29 is selected from hydrogen or alkyl groups, linear or branched alkenyl or alkoxy, substituted or unsubstituted, having from 6 to 20 carbon atoms, optionally containing one or more oxygen atoms, R30 is absent or hydrogen is selected or linear or branched alkylene, alkenylene or alkoxy groups, substituted or unsubstituted, containing from 1 to 6 carbon atoms, optionally containing 1 or more oxygen atoms, and G is selected from C02M, OSO3M, SO2OM, OPO (OM) 2 or P0 (0M) 2, wherein M is H, alkali metal cation, alkaline earth metal cation, ammonium, and mixtures thereof. 41.- The composition according to claim 40, further characterized in that said keto acid is selected from monooctylsuccinate, monododecyl succinate, 5-oxo-hexadecanoic acid, salts thereof or mixtures thereof. 42. The composition according to claim 1, further characterized in that the component of group (A) is a mercaptocarboxylic acid represented by the formula: O R 0CHCOM (XV) I SH wherein R40 is selected from C3_3alkyl or C3_3carboxyalkyl, and M is selected from hydrogen, alkali metal, ammonium, or mixtures thereof. 43.- The composition according to claim 1, further characterized in that the component of the group (A) is an organo acid substituted with amine of the formula: R3? N (R33) R32G (XII) 44. - The composition in accordance with Claim 1, further characterized in that the component of group (A) is a substituted amino acid of the formula: R35 I R34-C-C02M (XIII) i 1 R36-, N-R37 wherein R34, R35 3g and R37 are independently selected from hydrogen, alkyl, aryl, functionalized alkyl, aryl functionalized, alkanol, polyalkoxy, alkenyl, sulfur-containing portions or phosphorus-containing portions, or R34 and R3 may be covalently bound to form a cyclic amino acid, and M is selected from hydrogen, alkali metal, ammonium, organoammonium, or mixtures thereof. 45. The composition according to claim 44, further characterized in that said component is an amino acid selected from L-aspartyl-L-phenylalanine or a salt or methyl ester thereof. 46.- The composition according to claim 1, further characterized in that the component of group (A) is a substituted acid of the formula R38XR39G (XIV) 47.- The composition according to claim 1, further characterized in that said component of the group (A) is selected from nitrilotriacetic acid or a salt thereof, succinamic acid or a salt thereof, 4-hydroxybutyric acid or a salt thereof, dithiopropionic acid or a salt thereof, polyethylene iminoethoxylated dihydroxyacetone dimer, polyglyoxylate or a salt thereof, monoammonium maleate or diammonium maleate. 48. The composition according to claim 1, further characterized in that said component is a protein. 49. - The composition according to claim 48, further characterized in that said protein is a naturally occurring protein. 50.- The composition according to claim 49, further characterized in that said naturally occurring protein is selected from bovine serum albumin, bovine somatotropin, gelatin and casein. 51. The composition according to claim 1, further characterized in that said component of the group (A) is an organic acid. 52. - The composition according to claim 51, further characterized in that said organic acid is selected from phosphate or phosphonate present as free acids or salts thereof. 53. - The composition according to claim 1, further characterized in that two components of the group (A) comprising glutamic acid or a salt thereof, and borate are used. 54. - The composition according to claim 1, further characterized in that two components of the group (A) comprising polyaspartic acid or salts thereof, and polyacrylate are used. 55.- The composition according to claim 54, further characterized in that two components of the group (A) comprising polyaspartic acid of potassium and polyacrylate are used, and a component of the group is used. (B) which is selected from phosphate, borate, phosphonate, phosphite and hypophosphite. 56.- The composition according to claim 1, further characterized in that a component of group (B) is used. 57. - The composition according to claim 56, further characterized in that said component of the group (A) is an amide or polyamide selected from polyasparagine, urea, N-cocylglutamate or a salt thereof, succinic acid or a salt thereof , polyacrylamide, poly (2-ethyl-2-oxazoline), succinamide, polyaspartic acid, polyglutamic acid, maleamic acid, pyroglutamic acid, and salts thereof. 58.- The composition according to claim 56, further characterized in that said component of group (A) is an amino acid or polyamino acid selected from aspartic acid, asparagine, arginine, glutamic acid, ornithine, histidine, serine, glycine, polyglutamic acid, and you come out of them. 59.- The composition according to claim 56, further characterized in that said component of group (A) is a carboxylic acid or polycarboxylic acid selected from 4-hydroxybutyric acid, oxamic acid, polyglyoxylate, * 1,3,6-tricarboxyhexane, succinamic acid, lactic acid, tartaric acid, citric acid, malic acid, oxalic acid, maleic acid, acid 1,2,3,4- Butadienecarboxylic acid, N-phosphonomethylglycine, polyacrylic acid or formic acid, or salts thereof. 60.- The composition according to claim 56, further characterized in that said component of group (A) is selected from bovine somatotropin, bovine serum albumin, glycerol-2-phosphate or a salt thereof, 2-mercaptosuccinic acid or a salt thereof, dihydroxyacetone dimer, glutamine, dithiodipropionic acid and 2,4,6-trichlorophenol. 61.- The composition according to claim 56, further characterized in that said used component of group (B) is a borate. 62. - The composition according to claim 56, further characterized in that said component of group (B) is a phosphate or a phosphonate. 63. - The composition according to claim 62, further characterized in that said phosphate is an orthophosphate. 64.- The composition according to claim 63, further characterized in that said orthophosphate is selected from the group consisting of the monobasic, dibasic or tribasic salt, and mixtures thereof, having a cation selected from an alkali metal, ammonium ty and alkylammonium. * 65.- The composition according to claim 62, further characterized in that said phosphate, as its salt, it is selected from the group consisting of pyrophosphoric acid, metaphosphoric acid, hypophosphoric acid, phosphorous acid, polyphosphoric acid, and mixtures thereof. 66.- The composition according to claim 56, further characterized in that the component of group (B) is selected from (1-hydroxyethylidene-1,1-diphosphonic acid), aminotri (methylene phosphonic) acid, dodecyl-aminobismethylene phosphonic acid, acid hexamethylene-diaminotetra- (methylene phosphonic), diethylene-triamino-penta (methylene phosphonic) acid, N-phosphonomethylglycine, 2-phosphono-1,2,4-butanedicarboxylic acid, hydroxy-phosphonoacetic acid, salts thereof or mixtures thereof. 67.- The composition according to claim 61, further characterized in that a component of group (A) is selected from polyaspartic acid, aspartic acid, urea, lysine, poly (2-ethyl-2-oxazoline), L-glutamic acid , L-aspartic acid, citric acid, malic acid, 1, 3, 6-tricarboxyhexene, 1,2,4,4-transcarboxylic acid, or salts thereof. 68.- The composition according to claim 56, further characterized in that said component of group (A) is polyaspartic acid or a salt thereof, and a component of group (B) is selected from 1-hydroxyethylidene-diphosphonic acid, K-2B? .g0? or boric acid, or a salt thereof. 69. - The composition according to claim 61, further characterized in that a component of group (B) is used, and is selected from K-2B? OO? , boric acid, or a salt thereof. 70. A method for working metals, characterized in that said method comprises providing as a lubricant for said metals, an effective lubricating amount of a fluid lubricating composition in accordance with claim 1. 71.- The method for working metals in accordance with the claim 70, further characterized in that said metalworking comprises all metalworking operations that include metal formation and / or abrasion and / or metal removal. 72. The method for working metals according to claim 71, further characterized in that said metal work is formation. 73.- The method for working metals according to claim 71, further characterized in that said metal work is abrasion. The method for working metals according to claim 70, further characterized in that said method comprises feeding a water-soluble lubricating composition for working metals to a metal useful for receiving the same, comprising optionally diluting said water-soluble lubricating composition to work metals and feed the Water-soluble composition optionally diluted or undiluted to a portion of the metal by application (spraying or dipping), whereby said composition is effectively provided to said metal. 75.- The method of compliance with the claim 70, further characterized in that said fluid lubricating composition comprises the compositions according to claims 4 to 69. 76.- The composition according to claim 1, further characterized in that it comprises one or more corrosion inhibitors. The composition according to claim 76, further characterized in that the corrosion inhibitors are substituted and longer chain mono-, di- and tri-amines selected from 2,2'-ethylenedioxy-bis (ethylamine), trioctylamine , tris (2-aminoethyl) amine, polyethylene imine, N, N, N ", N ', -tetrakis (2-hydroxyethyl) -ethylenediamine, 4 (aminomethyl) -1,8-octanediamine, iminobis-propylamine or bishexamethylenetriamine. The composition according to claim 76, further characterized in that the corrosion inhibitors are lysine or ornithine 79. The composition according to claim Iß, further characterized in that the corrosion inhibitor is DIPSO (3- [N, -bis (2-hydroxyethyl (amino] -2-hydroxy-propanesulfonic acid). 80. - The composition according to claim 76, further characterized in that the corrosion inhibitors are imidazoles selected from 1-methylimidazole, 1- (3-aminopropyl) imidazole or 1,2-dimethylimidazole. 81. The composition according to claim 76, further characterized in that the corrosion inhibitor is triethanolamine. 82. An article of manufacture comprising a worked piece of metal or a piece of metal being worked, said work being or having been achieved by contacting or providing said metal, an effective amount of a fluid lubricant composition according to claim 1. 83. - The article of manufacture according to claim 82, further characterized in that said fluid lubricating composition comprises the compositions according to claims 4 to 69. 84. - The article of manufacture in accordance with claim 82, further characterized in that said metal surface being worked has been first cleaned and subsequently lubricated with said fluid lubricating composition. 85.- A method to reduce the wear of tools during the work of titanium metals or alloys thereof, wherein said metal work comprises working operations of metals that use a tool, by the use of a metalworking composition according to claim 1, wherein the component of the group (A) is a polycarboxylic acid or a salt or ester thereof. 86.- The method of compliance with the claim 85, further characterized in that said polycarboxylic acid is selected from the group consisting of polyacrylic acid, butacarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, undecanedioic acid , propanedicarboxylic acid, tartaric acid, sebacic acid, maleic acid, fumaric acid, citric acid, itaconic acid, citraconic acid, malic acid, aconitic acid and brazilic acid and tricarboxyhexanes, or salts or esters thereof. 87.- The method of compliance with the claim 86, further characterized in that said polycarboxylic acid is selected from 1,2,3,4-tetracarboxylic acid, succinic acid, or a salt or ester thereof. 88. The composition according to claim 1, further characterized in that the amount of a component selected from group (A) is on the scale of about 0.1% to about 75% by weight of the total composition *. 89.- The composition according to claim 88, characterized in that the concentration of the group component (A) is on the scale of about 0.25% to about 25% by weight of the total composition. 90. - The composition according to claim 56, further characterized in that when a component of the group (A) and a component of the group are used (B), the amount of a component selected from group (B) is on the scale of about 0.1 to about 60% by weight. 91.- The composition according to claim 90, further characterized in that the concentration of the component of the group (B) is on the scale of about 0.25% to about 15% by weight of the total composition. 92.- The fluid composition according to claim 56, further characterized in that more than one component of group (A) and / or group (B) is used. 93. - The fluid composition according to claim 62, further characterized in that a phosphonate is used as a component of group (B), and the concentration of the phosphonate is in the range of about 0.075% to about 50%. 94. - The composition according to claim 93, further characterized in that the concentration of the phosphonate is in the range of about 0.10% to about 15% by weight. 95.- The composition according to claim 94, characterized in that the concentration of the phosphonate is in the range of about 0.10% to about 10% by weight. 96. - The composition according to claim 1, further characterized in that the component of group (A) is a salt or mixtures thereof, or the component of group (B) is a salt or mixtures thereof, or both components of group (A) and group (B) are a salt or a mixture thereof, or no component of group (A) or group (B) is a salt. SUMMARY OF THE INVENTION This invention relates to novel water-soluble fluid compositions for working metals, their use for metal working, a method for working metals using said compositions, and the metalworking article of manufacture; more particularly, this invention relates to fluid compositions useful in cutting, abrading, shaping, and other working operations of metals that require a lubricant; the terms first group A and second group B are used in the present to denote different groups, and do not indicate any sequence of use or selection, since any possible combination or sequence of use of some component without limit of some kind is foreseen; The fluid compositions described are also anticorrosive and environmentally more acceptable than common oil-based fluids; a water-soluble fluid for working metals essentially odorless and substantially without oil mist formation has now been discovered, comprising at least one component selected from a first group A of the present and optionally one or more components selected from a second group B of the present, preferably the balance of the composition water and other optional minor ingredients; when a component of group A is used and a component of group B is used, the action of the combination improves generally the yield of the resulting combination containing portions of both group A and group B. 4 JN / MG / jhp * aom * asg * mmr * xal * mmm * mvh * xma * cgm * P99 / 52F