MXPA99008646A - Metal forming lubricant with differential solid lubricants - Google Patents

Abstract

A metal forming lubricant suitable for extreme condition use is formulated to contain one or more differential solid lubricants composed of a high melt temperature, substantially halogen-free thermoplastic in addition to conventional lubricants such as organic phosphate esters and natural and synthetic polymer waxes. The lubricants offer superior performance while resisting the tendency to foul metal working dies with gummy deposits. Conductive films may be prepared by including from 0.01 weight percent to about 2.5 weight percent conductive carbon black in the formulation.

Description

LUBRICANT FOR TRAINING ~ METAL (XM LUBRICANTS SOLID? DIFFERENTIALS TECHNICAL FIELD The present invention pertains to metal working lubricants. More particularly, the present invention pertains to aqueous lubricating, film forming compositions containing an organic lubricating phosphate ester, preferably a low melting lubricating polymer, and when less a high melting polymer, fl ured as dispersed phases. Lubricating compositions are especially useful in the setting of metals and similar operations, particularly cold forming and cold concentrating.

Prior Art In metal forming operations, the presence of a lubricant to work the metal is a necessity. Without a proper lubricant, the friction between the die and the work fold is so great as to cause galling, scratching and even tearing of metal. These problems are exacerbated in operations involving the formation of deep sections, for example > Two-piece metallic beverage cans, vehicle oil pans, and particularly thick-section products such as spark plug bases. In the past, articles of relatively shallow section could be coated with a lubricating oil film or a metallic coating, however, as the use of fewer stretch stages and stronger workpiece alloys pushed the In the processing envelope, these lubricants quickly became obsolete. In addition, the use of lubricating liquids and soft films does not lead to the manufacturing environment, the former due to its inherent fouling, and the latter due to the softness and hygroscopicity of the films produced, it has been found that the stearate and other fatty acid salts are problematic with respect to lifting operations, causing plugging of drains. These lubricants are also unable to be used in many modern metal forming operations where the surface temperatures of metal workpieces and dies can often exceed 500SC and can occasionally rise to temperatures of approximately 100? CC or higher due to both to the friction generated between the die and the work plate as well as the internally greased heat of the work due to the plastic flow of metal, at these temperatures and the high pressures associated with the formation of metal, even the High pressure "common, are completely ineffective. In addition to being lubricants under extreme operating conditions, an appropriate metal-forming lubricant must also possess other characteristics so that it can be used satisfactorily in a commercial establishment. For example, the lubricant should not accumulate on the die, otherwise way "breaks" or grooves can be formed. In some cases, the lubricant can form a residue of sufficient size so that the fully formed workpiece contains voids corresponding to the accumulation residue, and thus produce a part that is not the mirror image of the die. This is particularly the case with respect to inorganic bolide lubricants such as graphite, vermicuuta, molybdenum disulfide, and the like. Additionally, in most cases, it is desirable to coat the workpiece with lubricant away from the metal forming operation. For example, metal molds can be coated, dried and shipped to the metal forming plant by a supplier. In this way it is necessary that the lubricant coating be solid, not sticky, and not powdery. It is also necessary - that the lubricant coating be sufficiently hard to resist damage during handling and shipping. Particularly for ferrous metal parts, the coating should be relatively non-hydroscopic and should not contain salts that promote rust or corrosion. Examples of the latter are borates and nitrites, particularly the former, The preparation of lubricants with these often conflicting goals has proven difficult. In the U.S. Patent ,. No. 4,752,405 describes a lubricant containing a metal soap, in this case, an alkali metal salt of a? 2-3a fatty acid: a polyoxyethylene glycol having a molecular weight on the scale from 1500 Da to 8000 Da; an acrylic film forming polymer; and a variety of surfactants to promote complete mixing of the ingredients. However, while the dry films of the lubricant composition exhibited improved hardness, the films were still relatively higoscopic, absorbing only slightly less water than films having metal soaps and metal borates, such as films; and implemented by US Patent No. 3,725,274. It was believed that the absorption of water due to the use of polyoxyethylene glycols which are considerably hydrophobic therein. Metal and polyoxyethylene glycol soaps, even though they are excellent low temperature, low pressure lubricants, lose their lubricity at higher temperatures and pressures, and thus are not suitable for many modern deep drawing operations. In U.S. Patent No. 4,654,155, a water-bearing, water-bearing metal lubricant containing a complex organic phosphate ester, an amine, a pyoxyalkylated oil, one or more polyoxyalkylene glycol or polyester steres is disclosed. !, and a non-esterified polyoxyalkylene glycol. The composition was found to be highly lubricant by the three-ball test. However, the composition is only suitable for operations where liquid coatings can be tolerated, such as metal rolling operations. Additionally, none of the ingredients is a high temperature, high pressure lubricant. In the patent of E.U.A. No. 4,474,669 discloses a lubricant composition containing molybdenum disulfide, acrylic ester, acrylic acid polymer and a polyethylene wax in aqueous dispersion. The coating can be applied to a metal surface such as a beverage can mold. and drying-Boats formed with abero coated with lubricant by deep drawing compares favorably with cans formed from tin-plated steel in which the tin plating is naturally lubricant. However, the composition of US Pat. No. 4,474,669 contains molybdenum disulphide (moly.) Moly is widely known as a high pressure metal lubricant, however, it is very expensive and is currently a suspect. In this way, it must be recovered and disposed of appropriately or recycled, adding more to the manufacturing cost.The oly t mbié tends to leave deposits on the die, a variety of compositions that employ combinations of ea. polyethylene with polymers that form acrylic film with and without other ingredients such as organic phosphate esters Similar compositions containing polyvinyl chloride polymers instead of polyethylene are also known, such as those described in US Patent No. 3,725,274 It has been found that these compositions are suitable for modest embossing operations that do not involve high or exceptional temperature. high pressure Under the latter conditions, the films lose their lubricity. and excoriation, tearing and other effects occur regularly. Efforts to extend the scale of these compositions by adding lubricating polymers resistant to high temperature, such as polytetrafluoroethylene (PTFE, Teflon (R)), polyvinylidene fluoride, and the like have not been satisfactory. While the lubricity of some cases is satisfactory, it has been found that fluorinated polymers leave a residue that requires frequent cleaning and re-coating of the die. It would be desirable to provide the metal forming industry with a metal lubricant that can be used as a dry, durable coating; that is useful even at exceptionally high pressures and temperatures; that is environmentally friendly; which is substantially free of hygroscopic borates or metal soaps; and that it leaves very little residue on the metal dies. It would also be desirable to provide said liquid lubricant for those applications that do not require a previously applied coating. It would still further be desirable to provide metal coatings that leave a conductive residue on the formed parts.

SUMMARY OF THE INVENTION It has now been surprisingly discovered that excellent film forming lubricant compositions can be prepared which offer extended processing windows in the areas of high pressure and high temperature lubricity, combining organophosphate esters with conventional lubricant additives and at least one thermoplastic non-halogenated high melting point of modp that processing is possible at elevated temperature. The present compositions unexpectedly leave little residue on dies and other metal forming fixtures, unlike highly halogenated optics such as PTFE. Preferably, at least two thermoplastics are used that differ in operational scales (differential solid lubricants). The addition of lower amounts of conductive carbon black allows conductive coatings that are still within the acceptable processing windows.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The lubricant compositions of the present invention comprise a series of lubricating additives, each having its own scale of effectiveness. In lubricant compositions of the prior art, the selection of lubricant components has been made only with the end use in mind. For example, the organic phosphate esters and polyolefin waxes, both known lubricants, have been combined and tested to proposed operating conditions without regard to their action under any other conditions, even when not wishing to be limited to any particular theory, the Applicant believes that an appropriate metal working lubricant should provide lubricating capacity across a wide range of temperature and pressure, in addition to being only lubricants under extreme conditions, to be a metal forming lubricant under satisfactory extreme operating condition. While theoretically a component could demonstrate lubricity under the condition of low temperature, low pressure, and also extreme conditions, in practice said lubricant has not been identified »In this way it is necessary to employ a plurality of lubricants, each of which is capable to lubricate through a certain scale of conditions while ne interferes with the lubricity of other components of the composition. Aditionally, and again without wishing to be limited to any particular theory, the Applicant believes that the lubricity of a particular compound above its melting point is related to the capacity of film formation and / or viscosity under a given set of conditions. of operation. In this manner, the polyethylene wax, which is highly lubricant as a solid, remains lubricant at its melting point Y at temperatures higher up to a point where it no longer effectively produces a coherent film. This point may be related to viscosity, with the viscosity decreasing at higher temperatures preventing efficient film formation. It is believed that this is the reason why the polyethylene waxes and similar polymers are not lubricants under extreme conditions. Of course, the chemical structure of the additive and the adhesion between the additive and the metal surface that causes the structure is also a factor of lubricity. Organic phosphate esters and sulfurized oils, for example, exhibit lubricity on a broader scale than similar compounds, for example, non-sulfurized oils, despite having similar melting points and viscosities. It is believed due to the greater attraction that functional oils have with metal surfaces. Natural waxes such as montana, carnauba, etc., and polyalkylethyl waxes, such as polyethylene, low molecular weight polypropylene, ethylene vinyl acetate co-polymers, and the like, are natural candidates for lubrication films. . These waxes can be supplied in solvent form or as microemulsions and are dried to form slippery coatings. The addition of additives such as phosphate esters and their amine and ammonium salts increases the scale useful in terms of pressure. However, these lubricants provide smooth films unless they are combined with film formers, and lose their lubricity rapidly at elevated temperatures. Applicants have surprisingly found that metal working lubricants having a wide range of operation and suitable for extreme condition operation can be prepared by using lubricants of low to moderate condition in conjunction with one or more extreme condition lubricants comprising non-halogenated thermoplastics. of high temperature, finely dispersed. The use of lubricants of low to moderate condition such as polyoxyethylene glycols and similar polyoxyalkylene polyols and polyol esters; organic sulfates and phosphates such as polyoxyalkylene phosphates, triaryl- and tri (higher alkylene) phosphates; and natural and polymer waxes such as polyethylene waxes and poly (ethylene / vipyl acetate) copolymer allow the - 1_ > - present compositions are lubricants at low temperatures, while high temperature thermoplastics prolong lubricity at extreme conditions. The lubricity provided by high temperature thermoplastics is particularly surprising in view of the fact that a different from polyethylene, which has a natural slippery feel; and unlike halogenated thermoplastics such as PTFE, non-halogenated high temperature thermoplastics are not considered as lubricants at ordinary temperatures. In certain applications, it is desirable that any coating that remains on the workpiece after being formed is electrically conductive. Since the preferred compositions of the present invention are not hydrophilic and or substantially contain salts, they would be conductive after drying and after subsequent metal forming operations, unless a conductive constituent is added. The applicant has found that by adding conductive carbon black in lower amounts, ie, amounts of 0.001 to 0.25 parts per 10 parts of aqueous concentrate, and preferably from 0.005 to about 0.1 parts per 10 parts of concentrate. However, it allows conductive coatings to be prepared, while still maintaining the lubricity necessary for extreme metal forming operations. Surprisingly, the compositions containing conductive carbon black show slightly higher effectiveness in high temperature forming operations, despite the fact that carbide black, unlike graphite, is not considered to be lubricant. Suitable conductive carbon blacks are usually those with a pH greater than 6.0, and preferably in the range of 7.0 to 10.0, an absorption of dibutyl phthalate greater than 100 ml / 100 g, and a percentage of volatiles of less of 3% by weight, Appropriate conductive carbon blacks are available from numerous sources. A preferred carbon black is PRIísTTEX XB2, available from Degussa AG. The compositions of the present invention thus comprise one or more lubricants of low to moderate condition,? one or more non-halogenated polymers of high temperature, such as a dispersed phase. The present coating compositions, when desired for coating as a dry film, also contain minimally a film-forming polymer, and sufficient additives to stably disperse the polymer particles. The composition may also contain conventional additives such as antifoams, coalescing agents, anti-corrosion additives, etc. the composition preferably does not contain hygroscopic salts such as co nitrites or borates, ie, they are free of borate. In the liquid non-coating formulations of the present invention, the film-forming polymer may be omitted. In conductive formulations, the formulations contain conductive carbon black. The compositions of the present invention, as discussed above, are preferably free of borate, and are also generally free of hygroscopic salts having a t-enkehne to cause corrosion, including, in a non-limiting sense, borates, nitrates, nitrites, sulfates, chloride, alkali metal hydroxides, carbonates, bicarbonates, etc. Mediant "'substantially free of" with reference to said salts is given to understand that the composition does not contain any of said salts or the amounts present are impurities inevitable in the components of the system. In general; less than 2% of said salts by weight may be tolerable, since said amounts do not materially change the nature of 3, to composition. They do not increase so that lubricity can be measured on similar compositions that do not contain these salts, for example. The present lubricants are also preferably free of metal soaps, that is, metal salts of saturated and unsaturated acid grades - examples of which include alkali metal, alkali metal, torreous, zinc, etc. , salts of stearic and palmitic acids. It would not leave the spirit of the invention, as in the case of metal salts, to add the lower amounts of metal soaps that do not materially affect the basic nature of the lubricant, ie less than 2% by weight based on the weight of the product. concentrated. In this way, the compositions should be substantially free of metal soaps, and preferably completely free of said soaps. Lubricating compositions, by the same token, are preferably free of inorganic solid lubricants. By "inorganic solid lubricants" is meant lubricants which are inorganic and which are insoluble in water or in the prepared lubricant composition. Examples of such inorganic solid lubricants are vermiculite and mica, whether exfoliated or not; graphite; molybdenum disulfide, and other common inorganic solid lubricants. Again, it would not depart from the spirit of the invention to include a much lesser amount thereof, so that the material characteristics of the aqueous lubricant composition are not altered, the amounts of less than about 2-le - percent by weight, for example, meet this requirement, however, it is preferred that these ingredients are totally absent. It should be noted that the term "solid inorganic lubricant" does not include conductive carbon black. The present compositions, similarly, are also preferably free of hydrophilic colloids, carbohydrates, ie, starch, and other similar ingredients, which may increase water absorption, which may make sticky films dry, or which may be subject to to the development of a biological microorganism. By the term "low to moderate condition lubricants" is meant lubricants that are low melt point or liquid, and are suitable for use at temperatures and pressures up to and including the temperatures and pressures to which it is appropriate the polyethylene wax. One skilled in the art has no difficulty in selecting such lubricants, and can further be guided by the following list of lubricants of low to moderate condition which is and would be non-limiting. Examples of suitable moderate low pressure lubricants include mineral oil; lubricant oil; natural vegetable oil (triglycerides); sulfurized and phosphatized oils; organic esters such as alpha-alkyl glucosides, polyoxyalkylated alpha-alkyl glucosides; sorbitan oxyalkylates and orbitan esters; fatty acid esters; fatty acid amides; alkyl- and aralkylanes and long-chain polyamines; alkanolamines, particularly dialcanslamines and trialkanolatyins; natural waxes such as montana wax, carnauba wax, mineral wax (paraffin, polyoxyalkylene sulphate and phosphate esters) other complex organic sulphates and phosphates, polyoxyethylene glyols, polyoxypropylene glycols, tri-functional and higher polyoxyalkylene polyols, and their finished asynide group and derivatives of mono- and polyester; and polyalkylene waxes such as polyethylene homopolymer waxes and cspolymer waxes prepared by block and / or random polymerization of ethylene and other unsaturated monomers such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, methacrylate, methyl methacrylate, butylacrylate, maleic anhydride, styrene, alpha-methylstyrene cyclopentane, norbornene, and the like. Polyethylene waxes have melting points in the range of 70SC to 125SC Examples of organic phosphates can be found in the U.S. Patent, > 654, 135, which is incorporated herein by reference a) Organophosphate esters and some of the other low-to-moderate temperature lubricants cited, particularly those that have been functionalized with functional metalophilic groups, can exceed the lubricity of polyethylene waxes and similar compounds at elevated temperatures. Especially useful are combinations of low condition lubricants and moderate condition lubricants. Very often, the effectiveness of low-level lubricants overlaps or extends to the limits of the effectiveness of moderate-condition lubricants, for example, complex organic phosphates such as MASLIP < R) 504 are effective under low pressures and low temperatures where polyethylene waxes are not particularly effective, however, these phosphates maintain some effectiveness, even if limited, through most of the scale at which the waxes of efficient polyethylene. However, triisopropanol, an effective lubricant under low conditions, loses its effectiveness rapidly as temperatures and pressures increase. However, lubricants such as triisopropanplamine are still useful for their contribution of low pressure, low temperature, as well as for performing the function of solubilization and aiding in the dispersion of other ingredients. The critical component of the lubricants of the present invention is the non-halogenated thermoplastic polymer, high temperature. By "unhalogenated" term it is meant that less than 10 mole percent of the monomers used to prepare the polymer are halogenated monomers that substantially retain or retain the halogen fraction after polymerization. Examples of monomers halogenated are vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene and the like. Halogen-containing oils such as 4,4'-dichlorodiphenylsulfone, wherein the halogen is lost during the polymerization process, is not halogenated, the term "non-halogenated" also includes polymers free of halogen or substantially free of halogen-containing polymers. halogen which are subsequently halogenated, while not more than about 10%, preferably less than 5% by weight of the polymer consists of halogen.

It is preferred that the polymers be free of halogen, that is, they do not intentionally contain introduced halogen atoms. By the term "high temperature" is meant a polymer whose melting point is considerably higher than that of polyethylene wax and Polymers or polymers of polyethylene. that is, significantly greater than 200aC, preferably greater than 250SC. more preferably greater than 350 ° C, and more preferably, higher melting point. The polymer, however, must be thermoplastic, and must have a melting point, that is, it must melt before any substantial decomposition occurs. Polymers whose decomposition temperatures are lower than their melting temperatures are not useful unless said polymers comprise thermally stable block block polymers bonded together with one or more bonds that can be thermally decomposed. These polymers will have a melting point. block polymer segments that can be identified by Differential Scanning Calorimetry (DSC) preceded by a lower decomposition temperature. However, the modulus will remain at a higher value than that associated with a liquid, even at the decomposition temperature, until a substantial number of bonds are broken, essentially reducing a lower melting point polymer. The polymers will be essentially thermoplastic, that is, essentially molecules! linear that have minimal crosslinking. However, a "limited amount of crosslinking on purpose or not The non-limiting examples of suitable high-temperature thermoplastic polymers include polyamides, high molecular weight polyolefins, polyarylene sulphones, polyarylene oxides, and the like may be present while the polymers are still capable of melting and flowing at the temperatures and pressures used. polyarylene sulphide®, polyethersulfones, polyetherketones, polyimides, polyetherimides, polycarbonates, polyoxime ions, polyesters, and the like. Polyamides are particularly useful, in particular liquid crystalline polyamides and aramides. Polyamides with melting points on the scale of 200 to 300 ^ C, ie polyamide 66, can be useful at the lower end of the extreme lubricant scale, and much more stringent conditions than polyethylene waxes and the like. However, the extension of the processing parameters of the present lubricants to extreme conditions requires the use of liquid crystalline polyamides, aramides, or other high-melting polyamides. Preferably, the polyamides have a melting temperature of 300 ° C. or higher, preference 3502C or greater. Such l-aer aramides of Nomex (R) and evlar () have high melting temperatures (m), for example, on the scale of 365 ° C to 500 ° C., These polyamides are commercially available. High temperature polyolefins are also useful. Unlike polyethylene waxes that are oligomeric and often contain additional comonomers to further reduce melting points, high temperature polyolefins are prepared using catalyst systems that aid in high molecular weight and structural uniformity, which results in these Polymers have high melting points, Polyethylene and ultra high molecular weight polypropylene, particularly polypropylene having a high degree of isotacticity may be appropriate. However, in particular, polymers of cyclohexene, cyclopentene, norbornene and the like, optionally substituted with appropriate alkyl groups, as well as their copolymers. These polymers are commercially available. For example, isotactic poly (3-methyl-1-butane) and isotactic poly (4-methyl-1-pentene) have melting points (Tm) of 310aC and 2402C, respectively. . An arrangement containing high melting temperature polyethylene is available as SLIP-AYD 635 from Daniel Products. Polyarylensulfoas, polyether ketones and polycarbonates are characterized by the repeating structure: - [0-X-0-Y] n wherein each 0 represents the same or a different aryl fraction such as, but ho limited to, substituted and unsubstituted phenyl , biphenylene, naphthyl, diphenylether, diphenylmethane and diphenylisopropylidene, wherein the preferred substituents are C14 alkyl groups, and wherein X and Y are the same or different, and represent -O-, -S-, -SO-, '-SOr -, -CD- *, O-CO-O, and the like. These thermoplastics are readily available commercially. Polyesters are also useful. The polyosters are derived from the esterification by condensation of a diacid and a glycol. Both conventional polyesters and liquid crystallines are useful. Examples of polyesters are high molecular weight polyethylene dipates, polybutylene adipates, polyethylene terephthalates. { Tffl = 245SC), polibu ílenteref alatos, polycyclohexandimetile erefta-latos, etC >; Again, these polyesters are available commercially available. The polyimides and polyetherimides are additionally useful. Examples of polyimides with Kapton (R) and Lenzing 2080. An example of polyetherimide is Ultern (R), a product of General Electric, El. High temperature thermoplastic should be used in finely divided form so as to result in a stable dispersion. These dispersions are preferably resistant to sedimentation of solid components for at least several days without agitation. The polymers can be supplied in the form of fibers or fibers that are cut into fibers of relatively low aspect, ie, fibers having a ratio between dimensions (length: diameter) of from about 10: 1 to about 1: 10, between more iino is the diameter of the fiber < The ratio between dimensions that can be tolerated is higher. For example, with icroh and submicron-sized fibers, ratios with dimensions as high as or greater than 20-10Ó: 1 can be tolerated- Recently, a special form of fibrous fiber has evolved (R) fibrous has been developed that is highly appropriate These fibers, known as fevlar (R) 1F543, have been used for use as thickeners and thixotropic agents, and have numerous icrofiber tendrils outside the main fibers which gives them a particularly high surface ratio. High temperature thermoplastic polymers they can also be used in finely divided form produced by such techniques as gas jet mill, sand grinding, cryogenic milling, spray drying, solution precipitation and the like. For example, a particular polymer can be dissolved in a "solvent miscible in strong water, aprotic, such as N-oxyethylpyrrolidone, dimethylchloride, d.methylacetamide, or dimethylformamide, and pour into water, or other non-solvent with which the aprotic solvent is miscible, under high shear agitation to produce icroparticles "generally spherical or elongated polymer, particle sizes from 0.05 um to 50 um, preferably 0.1 um to 10 um are preferred. The high temperature thermoplastic may be present? amounts ranging from about 01. percent by weight to about 20 percent by weight based on the weight of non-volatile ingredients, give preference of about 1 percent by weight to about 10 percent by weight. Higher percentages may be useful when two high temperature thermoplastic polymers are used extending to two temperature scales. For example, an extended scale lubricant composition may have low temperature / pressure lubricants such as triisopropylamine and MASLlP phosphate ester. ? R), a lubricant such as SLIP * -AYD (R) 63? Ua polyethylene wax and high melting temperature polyethylene dispersion available from Daniel Products; an extreme condition lubricant, elevated temperature / pressure of nylon 44 or nylon 46 or fiber particles, and a very high temperature / pressure extreme condition lubricant of Kevlar (R) fibrils, in the film forming compositions of the present invention, the ingredients contain u? film forming polymer. The film-forming polymer is one that is soluble or dispersible in the remaining ingredients, which preferably forms a substantially non-tacky film when dried, the film being relatively hard, the appropriate film-forming polymers are well known and include various polyacrylates, polyvinylaclates, styrene-acrylic copolymers, polyurethanes, and the like. An example of a suitable film-forming polymer is JONCRYL (R) 678 acrylic resin, a product of S.C. Johnson & They are believed to contain 1-3 weight percent of diethylene glycol monoethyl ether and a styrene-acrylic copolymer. The JONCRYL (R) -6 8 is nominally a solid in the form of transparent scales, has an acid value of 200, a density of 1.25 g / cm3, and a number-average molecular weight of about 800. However, the polymer of particular film formation is not especially critical. film "are those capable of being molded as a film from aqueous solution, emulsion or dispersion, and do not include polymers that can only be extruded or emptied into organic solvent, v.gr ,, PTFE." The film, as indicated, is preferably not sticky or substantially non-tacky By "substantially non-sticky" it is implied that the degree of tackiness or tackiness felt by a touch is "at best small. However, some stickiness can be tolerated, particularly if the lubricant is to be applied to the workpiece in the same construction and can be protected from dust or grime collection. Under these conditions, if you want a low degree of tackiness, the film should also be relatively hard, so that it does not scratch, abrade or remove easily during routine handling. Those skilled in the art easily understand the meanings of the terms "tackiness," "substantially tack-free," "hard" in relation to the hardness of the film, and the like, If the lubricant use of the present invention is Liquid state can be tolerated, then the film-forming polymer or a portion thereof can be removed from the formulation. However, in such cases, it may be advisable to introduce a soluble polymeric thickener, for example, a conventional polyacrylic acid thickener or an association thickener such as those described in US Patents. Nos, 4,709,099; 4,673,518; 4,665,239; 4,649,224; and 4,354,956 in order to increase the viscosity to aid in the application and maintenance of the coating. For example, it may be desirable to use a lubricant having the composition of a cream or gel, or which is thixotropic. Additionally, sufficient film forming material or an equivalent is necessary to act as an adhesion agonist to promote adhesion of the lubricant composition to the workpiece. Additional ingredients including anti-corrosion agents, other pressure reducing additives, and lubricity aids such as those described in US Patents. 4,390,433; 4,493,780; 4,626,366; and 4,797,299, which are incorporated herein by reference. Preferred compositions are concentrates containing, based on solids, from about 0.5 weight percent to about 20 weight percent, more preferably from about 1 weight percent to about 10 weight percent of a polymer. film formation, from 0.1 weight percent to about 20 weight percent, more preferably from 1 weight percent to about 10 weight percent of an organic phosphate ester; from 0 weight percent to about 30 weight percent, more preferably from 1 weight percent to about 20 weight percent of one or more polyethylene or similar low melting waxes; and from 0.1 weight percent to about 20 weight percent, more preferably from 0.1 weight percent to about 10 weight percent of at least one high melting point heat. The conductive carbon black, when used, is preferably in the range of about 0.01 weight percent to about 2.5 weight percent in that- most preferably, 0.01 weight percent to about 0.5 percent in weight. weight . The concentrations thus formed can be diluted to a ratio of 0.5 parts of concentrate to 99.5 parts of water, more preferably, a ratio of concentrate to water of 5:95, still more preferably 10:90, and advantageously 30:70. . The upper or lower dilution may be used, as desired. Having generally described this invention, further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting, unless otherwise specified.

EXAMPLE 1 A film forming metal working lubricant composition is prepared by thoroughly mixing the following ingredients until a stable, uniform dispersion results. The parts by weight are of the components as supplied. Ingredient Parts in Weight 1. SLIP-AYD (R) SL 630 62. 2. JONCRYL (R) 537 24 3. - MASLIP (R) 504 3.6 4. ÁGRÓSOL OT 75 ~~ 0.5 5. "Triisopropanolamine 0.Ó 6.". BYK 032 0.24. Water 8, 8 8. High Temperature Lubricant Polymer (Kevlar (R) and / or SPECTRA (R) Fibers) 0.1 to 20 Ingredient 3 was cut to ingredient 2 until a homogeneous mixture resulted. Ingredients 4, 5 and 6 were mixed together with gentle stirring (mixed in.), After which the ingredient 7 is added. The mixture of ingredients 4-7 is then subjected to shear with the mixture of = and 3 until what is homogeneous, The ingredient 8 is mixed with the ingredient 1, after which the mixture is mixed with gentle agitation with the preceding ingredients. "The amount of high temperature polymer depends on the end use, with higher amounts, that is, .5% by weight to 10% in £> that or more appropriate for 'cold forged Oh while the lower amounts, Or say, 0.1 to 5%, are suitable for embossing and stamping operations, A formulation as above, and containing 0.5-40% by weight of Kévlar (R) 1F542 fibers is compared to a similar product that does not contain Kevlar (R) .The Kevlar (R) formulation produced a superior product.The formation compared to a teflon-containing lubricant is superior as the teflon-containing lubricant forms a coating on or over the die after various uses.

Example 2 In the same manner as Example 1, a "concentrate was prepared from the following ingredients: 5.62 parts SLIP-AYD 630 2.16 parts JONCRYL 537, 65 parts Phosphate Ester MASLIP 504 .08 parts CYTER PT75, or Agent Scatter Dispersed AYD W22 .08 parts friisopropanolamine .02 parts Antifoam BYK 032 .9 parts Tension Modifier ~ Dapro W9 HS (Daniel * Products) 79 parts Water , 3 parts Total The concentrate showed excellent lubrication of cold forming and cold forging at dilutions of 10:90 and 30:70.

EXAMPLE 3 To the concentrate of Example 3, 0.05 parts of Deguesa's PRINTEX XE2 carbon black is added. The lubricity is not as high as the lubricant of Example 2, but is comparable to or superior to commercial lubricants that do not contain carbon black. Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications may be made thereto without departing from the spirit or scope of the invention as set forth herein.

Claims (20)

CLAIMS:

1. - An aqueous metal lubricant, suitable for extreme condition lubrication in metal forming operations, comprising: an organic phosphate ester lubricant; and dispersed therein, one or more substantially finely divided, high melting temperature, halogen-free thermoplastics having a TB of about 200s or greater, the aqueous metal lubricant substantially free of borates.

2. The lubricant of claim 1, wherein the high melting temperature thermoplastic has a Tm greater than about 300SC.

3. The lubricant of claim 1, wherein the high melting temperature thermoplastic has a TB greater than about 400-C.

4. The lubricant of claim 1, which comprises at least two high-melting temperature optics, substantially free of halogen, differing by Tm by at least 50aC.

5. The lubricant of claim 1, comprising at least two thermoplastics of high melting temperature, substantially free of halogen which "differ in at least 10 aC.

6 - The composition of claim 1, further comprising a film-forming polymer that during the evaporation of water leaves a film that is substantially non-sticky and non-hygroscopic.

7. The composition of claim 1, wherein at least one or more high melting temperature thermoplastics, substantially free of halogen, is selected from the group consisting of an aramid having a Tm greater than 350aC and a polyolefin. having a T greater than 250 ° C,

8, The composition of claim 6, comprising: a) from about 2.5 to about 35 weight percent of the film-forming polymer; b) from about 0.5 weight percent to about 20 weight percent of a polyoxyalkylene phosphate ester as the organic phosphate ester lubricant; c) from about 0.1 to about 2U percent by weight of one or more high Ta thermoplastics, substantially free of halogen, having a melting temperature Tm greater than about 20O2C as at least one or more thermoplastics of high melting temperature.; and further comprising: d) from about 2.5 to about 35 weight percent of a natural or synthetic wax having a melting point of about 125SC or lower; and optionally, e) from 0 to about 20 weight percent of one or more dispersing-stabilizing and / or coalescing promoting surfactants.

9. The composition of claim 1, further comprising about 0.01 weight percent to about 2.5 weight percent based on the total weight of the composition, of conductive carbon black.

10. A dilute metal forming lubricant comprising the lubricant of claim 1, diluted with 1 part about $ 9 parts of water per part of the lubricant of claim 1,

11. An aqueous metal lubricant suitable for lubrication in extreme condition in metal forming operations, comprising: an organic phosphate ester lubricant; and dispersed therein one or more finely divided, high melting temperature, substantially halogen-free thermoplastics having a T of about 200s or greater, the aqueous metal lubricant substantially free of metal soaps.

12. - The lubricant of claim 11, comprising at least two thermoplastics of high melt temperature, substantially free of halogen, differing in T »by at least 50 ° C.

13, - The composition of claim 11 < It also comprises a film-forming polymer which, during the evaporation of water, leaves a film that is substantially non-sticky and non-hygroscopic.

14. The composition of claim 13, comprising: a) from 2.5 to about 35 percent by weight of the film-forming polymer; b) from about 0.5 weight percent to about 20 weight percent of a polyoxyalkylene phosphate ester as the organic phosphate ester lubricant; c) from 0.1 to about 20 weight percent ® one or more high Tm thermoplastics, substantially free of halogen, which has a melting temperature B greater than about 200aC as at least one of the one or more thermoplastics of high melting temperature; and comprising further: d) from 2.5 to about 35 weight percent of a natural or synthetic wax having a melting point of about 125aC or lower; and optionally, e) from about 20 weight percent of one or more dispersion-stabilization and / or coalition promoting surfactants.

15. The composition of claim 11, further comprising about 0.01 weight percent to about 2-5 weight percent, based on the total weight of the composition, of conductive carbon black.

16. A metal lubricant suitable for extreme condition lubrication in metal forming operations, comprising: a lubricant of organic phosphate; and dispersed therein, one or more thermoplastics substantially free of halogen, of high melting temperature, finely diVidides, having a T "of about 200a or greater, the aqueous metal lubricant substantially free of inorganic solid lubricants.

17. The lubricant of claim 16, comprising at least two thermoplastics substantially free of halogen, of high melting temperature, differing in Tm by at least 50aC.

18, - The composition of claim 16, further comprising a film-forming polymer that during the evaporation of water, leaves a substantially non-sticky and non-hygroscopic film.

19. The composition of claim 18, comprising, a) from 2.5 to about 35 weight percent of the film-forming polymer; b) from about 0.5 weight percent to about 20 weight percent of a polyoxyalkylene phosphate ester as the organic phosphate ester lubricant; c) from 0.1 to about 20 weight percent of one or more substantially halogen-free, high-temperature thermoplastics having a melting temperature t? greater than about 200SC as At least one of the one or more high melting temperature thermoplastics; and comprising e a: d) from 2.5 to about 35 weight percent of a natural or synthetic wax having a melting point of about 125aC or lower; and optionally, e) from 0 to about 20 weight percent of one or more dispersion-stabilization and / or co-promotion promoting surfactants.

20. - The composition of claim 16, which further comprises about 0.01 percent by weight to about .5 percent by weight, based on the total weight of the composition, of conductive carbon black.