WO2022099300A1

WO2022099300A1 - Metalworking formulations with corrosion inhibitor formulations

Info

Publication number: WO2022099300A1
Application number: PCT/US2021/072259
Authority: WO
Inventors: Howard Wong
Original assignee: Ardagh Metal Beverage USA Inc.
Priority date: 2020-11-05
Filing date: 2021-11-05
Publication date: 2022-05-12
Also published as: EP4240819A1; US20240026245A1

Abstract

Metalworking formulations and corrosion inhibitor formulations are provided. The metalworking fluids have excellent performance as coolants in the manufacture of thin-walled metal containers such as aluminum beverage cans.

Description

METALWORKING FORMULATIONS WITH CORROSION INHIBITOR FORMULATIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/110,302, filed November 5, 2020, the contents of which are incorporated by reference in their entirety.

FIELD

[0002] The present disclosure relates to metalworking formulations and corrosion inhibitor formulations. The present disclosure also relates to metalworking compositions used as coolants and/or lubricants in the manufacture of thin-walled metal containers such as aluminum beverage cans.

BACKGROUND

[0003] Metal containers, such as aluminum cans, can be formed by industrial machinery. Light-weight aluminum containers made of high-strength alloys can be produced from coiled metal sheets using can manufacturing machinery that includes a cupper and a bodymaker. A metal sheet is unwound from a coil and undergoes a first operation for cupping which includes blanking and drawing; more specifically, during this step, the coil of sheet feeds a press, also known as a cupper, which cuts disks known as blanks and performs a first deep-drawing operation to produce cups. The cups are then conveyed to a second press or bodymaker where they undergo at least one second deep drawing operation and a plurality of successive ironing operations; these consist of passing the deep-drawn blank through ironing tools, known as rings or dies, in order to elongate and thin the metal. The bodymaker performs a series of wall ironing operations to sequentially reduce the diameter and wall thickness, and increase the height of the container to its appropriate height, diameter and wall thickness. The wall ironed container can then be trimmed, necked and finished as desired.

[0004] Through these cupping and bodymaking operations, one or more metalworking fluids are employed for cooling and lubrication. A cupping lubricant is employed in the cupper, and some portion of the cupping lubricant remains present as the workpieces move to the bodymaker. At the bodymaker, an additional metalworking fluid designed for cooling (a coolant) is applied to reduce the temperatures of the workpieces and the equipment. The coolant may provide additional lubricity, particular if the amount of remaining cupping lubricant is low or minimized. [0005] More generally, metalworking fluids are commonly employed to provide cooling and/or lubrication to both the workpiece and the metalworking apparatus in a variety of metalworking operations, including but not limited to cutting, forming, drawing, ironing, stamping and rolling. The metalworking fluids may also be used to flush away oil and debris from the worksite, and/or provide corrosion protection to both the workpiece and the metalworking equipment. Metalworking fluids have comprised oil-based materials or emulsions of water and oil, but it has long been desirable to replace oil-based products with water-based materials. The use of water-based metalworking fluids has become widely used.

[0006] Water-based metalworking fluids should provide good lubricity to the workpiece and metalworking apparatus, facilitate cooling of the workpiece and apparatus which may operate at high temperatures, and collect and remove debris and contaminants, including oils, from the worksite. In addition, water-based metalworking fluids should provide good corrosion protection to both equipment and workpieces. In pursuit of these objectives, various water-based metalworking fluid compositions have been developed; however, various disadvantages have arisen with the use of many existing compositions. [0007] Water-based metalworking formulations have been made by combining several separate ingredients that are known, individually, to have lubricating functions. For example, various oils, block copolymers, liquid crystal formers and surface active agents have been combined and provided to the final users as blended products.

[0008] Metalworking compositions are often produced as concentrated formulations which can be diluted prior to use. Concentrated metalworking compositions are prepared by the manufacturer and shipped in drums to the user, who may store the drums of concentrated formulation for weeks or months prior to use. Because the lubricant properties of the metalworking composition may be lost if the metalworking composition deemulsifies or separates, the concentrated metalworking composition should have a shelf life (stability, i.e., time before deemulsification or separation occurs) at room temperature (about 25°C.) of at least one month, or at least six months, or at least one year, or at least two years. The high temperature (about 45°C. or 50°C.) stability and the low temperature stability (about 0°C.) should each be for weeks or months. Following dilution of the concentrated metalworking composition, the resulting diluted metalworking composition should have a shelf life at room temperature of at least one month, or at least six months, a high temperature stability of at least one day and a low temperature stability of at least one day.

[0009] As noted above, it is desirable for a metalworking fluid to reduce or prevent corrosion. Some prior metalworking compositions include phosphate esters or borate esters as corrosion inhibiting components. Phosphate esters include aromatic phosphate esters such as tricresyl phosphate, alkyl phosphate esters such as tributyl phosphate, thiophosphates and metal containing phosphate esters such as zinc dialkyldithio-phopsphates (ZDDP). Both phosphate esters and borate esters provide improved stained resistance and corrosion resistance by forming a hydrophobic film on aluminum and ferrous surfaces, thereby preventing water from contacting the surface. However, boric ester components leave a thin film behind, and phosphate ester components potentially react with aluminum when the surface is sufficiently hot. Its reaction product may be difficult to clean off the surface, which poses special problems when used in manufacture of thin-wall metal containers, particularly aluminum beverage cans. Metal cans typically have various lacquer coatings to the can surface, and the presence of a residual film or reaction products could give rise to high metal exposure in the can and increase the propensity for holes since the lacquer is supposed to protect the can surface from the beverage.

[0010] Can manufacturing machinery operates at high speeds and temperatures, and the machinery has its own requirements for lubrication. Gear oil is used as a high viscosity lubricant in various machinery, including the cupper and bodymaker of can making machinery. Gear oil usually contains high molecular weight hydrocarbon components, as well as organosulfur and/or phosphate compounds or other inorganic compounds as extreme pressure (EP) additives or antiwear additives. Metalworking fluids used for coding workpieces in can making may contain adventitious gear oil components from the bodymaker or cupper. Such components may contribute to the lubricity of the fluid, but they leave residue on can surfaces and are difficult to clean.

[0011] Whereas numerous metalworking fluids based on both unmodified and modified triglycerides have been developed, there is a continuing need for new metalworking formulations, which may have one or more economic advantages and/or performance advantages. Performance advantages can include greater ability to effectively formulate the metalworking fluid. It can also include improvement in one or more of the properties of the metalworking fluid. It is particularly effective if these improvements are achieved without adversely affecting the other properties of the metalworking fluid.

[0012] In all metal working operations it is necessary to lubricate the interface between the workpiece and the tool to decrease the force required to work the metal; to cool the work-piece; to remove chips from the cutting zone; to impart a good surface finish; and to extend the life of the tool. The formulation of metalworking compositions is challenging, because a wide variety of compounds may be used, as, for example, antifriction agents, anticorrosion agents, surfactants, and biocides.

[0013] There is also a need for concentrated and diluted metalworking compositions that are stable for longer periods so that they can be produced and stored for longer periods of time prior to use.

[0014] There is a need for metalworking formulations that provide cooling and lubricity but less residue and easier cleaning, particularly when used as a coolant fluid for the manufacture of thin-walled metal containers such as aluminum beverage cans.

SUMMARY

[0015] As one aspect of the present invention, a metalworking formulation comprises an esterified lubricity additive; a block copolymer; an amine; and a corrosion inhibitor formulation. The corrosion inhibitor formulation comprises an acyl amino acid derivative of formula la, lb or Ic (which are defined herein). In some embodiments, the corrosion inhibitor formulation further comprises a succinic acid derivative, a triazole, a C6-C20 branched carboxylic acid, a sugar alcohol, an imidazoline, or a mixture thereof. An advantage of some embodiments of the present formulations is that they do not significantly stain aluminum. Another advantage of some embodiments is that the formulation is substantially free of phosphoric acid derivatives such as phosphate esters, substantially free of boric acid derivates such as borate esters, and/or substantially free of corrosion inhibiting components that are film-formers on metal surfaces. Yet another advantage of some embodiments is that the formulation is stable at temperatures between 0°C and 45°C or between 0°C and 50°C. In some embodiments, the formulation has a cloud point temperature of at least about 45°C, or at least about 50°C. Another advantage of some embodiments is a formulation that is ashless or consists essentially of ashless components. For instance, such formulations can degrade to low molecular weight degradation products. [0016] As another aspect of the present invention, diluted metalworking compositions are provided. The diluted compositions comprise any of the metalworking formulations described herein, in an amount effective to provide lubricity, and a diluent. In some embodiments, the diluent is water, and the amount of the metalworking formulation in the diluted composition is from 0.5% to 10% w/w, or from 1% to 8%, or from 2.5% to 6.5%.

[0017] As yet another aspect of the present invention, a corrosion inhibitor formulation for inhibiting corrosion of iron and aluminum is provided. The corrosion inhibitor formulation comprises (a) an acyl amino acid derivative of formula la, lb or Ic (which are defined in detail below); (b) an amidated succinic acid derivative and/or a water soluble succinic ester with amine; and (c) a triazole. The formulation can provide ferrous and aluminum corrosion resistance.

[0018] As another aspect, a method of making a thin-walled metal can is provided. The method comprises the steps of (a) forming a metal disk; (b) drawing the metal disk to form a shallow cup; (c) applying a metalworking formulation (as described herein) to the shallow cup;

(d) redrawing and wall ironing the shallow cup to form a thin-walled tubular can body having an open end and an opposing closed end; and (e) washing the metalworking formulation off the thin-walled tubular can body. In some embodiments, steps (c) and (d) are performed without applying a hydrocarbon-based lubricant. Alternatively, in some embodiments, steps (c) and (d) are performed by applying a mineral oil at no more than 1 wt. % of the metalworking composition. In some embodiments, step (c) is performed in a bodymaker, and the metalworking formulation rejects gear oil components from the bodymaker, and/or step (b) is performed in a cupper, and the metalworking formulation rejects gear oil components from the cupper or the coil.

[0019] These and other features and advantages of the present formulations and methods will be apparent from the following detailed description, in conjunction with the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIGs. 1 to 9 shows results from Microtap testing of various examples for lubricity.

[0021] FIG. 10 is a graph showing pressure drop across a fdter when an embodiment of the present metalworking composition was used.

[0022] FIG. 11 shows photographs of filters used for cleaning coolant fluids which have been used on a bodymaker.

[0023] FIG. 12 shows photographs of a drip pan beneath conveyors in an aluminum can manufacturing line.

[0024] The present teachings are best understood from the following detailed description when read with the accompanying drawings. The features are not necessarily drawn to scale.

Wherever practical, like reference numerals refer to like features. DETAILED DESCRIPTION

[0025] As one aspect of the present invention, improved metalworking formulations are provided. The metalworking formulations comprise an esterified lubricity additive; a block copolymer; an amine; and a corrosion inhibitor formulation. In some embodiments, the corrosion inhibitor formulation comprises an acyl amino acid derivative of formula la, lb or Ic:

R1..(C0)-N(R²)— (CH₂)H— CO2X la

[R'-(CO)-N(R²)— (CH2)n-CO₂]_mY lb

[R¹-(CO)-N(R²)— (CH2)n-CO2]m-Z-(OH)_P Ic where R¹ is Ce-Cso optionally substituted alkyl or G.-Cso optionally substituted alkenyl, and R² is hydrogen or C1-C4 alkyl; X is hydrogen, C1-C30 optionally substituted alkyl, or a C2-C30 optionally substituted alkenyl group; Y is an alkali metal or an alkaline earth metal; Z is a residue remaining after removal of a hydroxyl group from a polyhydric alcohol; m is an integer of 1 or greater, which is 1 when Y is an alkali metal and 2 when Y is an alkaline earth metal; p is an integer of zero or greater; n is an integer of 1 to 4, and m+p is the valency of Z. In some embodiments, the acyl amino acid derivative is oleyl sarcosine.

[0026] The formulations comprise an esterified lubricity additive, such as a water dispersible esterified dimer or trimer acid. Water dispersible esterified dimer or trimer acids can be the esterification product of: (1) an acid component comprising a dimer acid, a trimer acid, or a mixture thereof; and (2) an alcohol component comprising an alkylalkoxy alcohol, optionally in combination with an alkyl alcohol. Esterified dimer and trimer acids are discussed in Bingeman U.S. Pat. App. Pub. No. 20050037933 Al, and examples include Priolube 3952 and 3955 (available from Croda). In some embodiments, the acid component is a mixture of relatively high weight carboxylic acids, such as 36-carbon dimer acids and 54-carbon trimer acids. Component structures may be acyclic, cyclic (monocyclic or bicyclic) or aromatic. Dimer and trimer acids are commercially available from various sources, such as Pripol 1040 or 1045 from Croda, and can be esterified.

[0027] Water dispersible ETAs can have ionic and/or non-ionic surfactant activity. To provide anionic surfactant activity of the ETA in water, an anionic group (such as a carboxylic acid) of the ETA is neutralized with a base. This neutralization of the ETA leads to the formation of the water dispersible ETA. Any base can be utilised as a neutralization agent in the production of the water dispersible ETA, e.g. sodium or potassium hydroxide may be suitable. Typically an amine such as triethanolamine (TEA) will be used as the base; other amines are discussed in detail below, which are also suitable for combining with ETAs.

[0028] Other suitable esterified lubricity additives are disclosed in Bingeman et al. US Pat. App. Publication No. 20150225666 Al as compounds of formula III:

III where R9 is

where m=3-12, n=3-8 and R¹⁰ is

where x=l-50, y= 1 -100 and R11 is C1-C16 optionally substituted alkyl, such as a secondary alkyl.

[0029] Other suitable esterified lubricity additives are partial or half-esters of a compound derived from the Diels-Alder reaction of a conjugated fatty acid and an acid precursor dienophile, such as AltaLUB 5300 (available from Ingevity, North Charleston, SC). Suitable partial or half-ester lubricity additives as described in Cuff et al. US Pat. App. Publication No.

20170107440 Al, which include compounds of formula IV:

wherein R11 and R12 are independently selected from the group comprising H, alkyl, alkenyl, cycloalkyl, chloroalkyl, chlorocycloalky, polyoxyethylene, polyoxypropylene, or a mixture thereof, and wherein at least one of R1 and R2 is H and the other is not.

[0030] The esterified lubricity additive can be included in the metalworking formulation at any amount suitable to provide desired lubricity. The amount of the esterified lubricity additive can be at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 4.5%, or at least 5%, or at least 5.5%, or at least 6%, or at least 6.5%, or at least 7%, or at least 7.5%, or at least 8%, or at least 9%, or at least 10%, or at least 11%, or at least 12%, or at least 13%, or at least 14%, or at least 15%, or at least 16%, or at least 17%, or at least 18%, or at least 20%; or the amount can be at most 40%, or at most 35%, or at most 30%, or at most 25%, or at most 22%, or at most 20%, or at most 19%, or at most 18%, or at most 17%, or at most 16%, or at most 15%, or at most 14%, or at most 13%, or at most 12%, or at most 11%, or at most 10%, or at most 9.5%, or at most 9%, or at most 8.5%, or at most 8%; it is contemplated that any of these minimums and maximums can be combined to form a range (so long as the minimum is lower than the maximum).

[0031] The present metalworking formulations also include a block copolymer. Block copolymers (BCP), and in particular reverse block co-polymers (RBCP), are well known for use in metal working fluids, where they act as lubricants and often as surfactants. For instance, metalworking fluids comprising a water-soluble mixture of block copolymers are discussed in Laemmle US Patent 4,452,711 and Lorentz et al. US Patent 6,806,238.

[0032] Block copolymers are polymers comprised of subunits which are themselves polymers. For instance, block copolymers can have the structure XXXX-YYYY-XXXX, wherein X and Y are repeating units. Block copolymers may have more complex structures, such graft copolymers or comb copolymers. Suitable block copolymers for the present formulations include polyoxyalkylene copolymers, such as where the polyoxyalkylene blocks comprise or consist essentially of polyoxypropylene (PO) and polyoxyethylene (EO) repeating units. The polyoxyalkylene blocks may be randomly arranged within the block copolymer or they may be arranged alternatively.

[0033] In some embodiments, the block copolymer comprises a structure represented by formula (Ila), (lib) or (lie):

R³-(EO)x-(PO)_y-R⁴ Ila R³-(EO)x-(PO)_y-(EO)z -R⁴ lib

R³-(PO)x-(EO)y-(PO)z -R⁴ lie where R³ and R⁴ are independently selected from -H, -OH, -(CR⁵R⁶)_WH, or -(CR⁵R⁶)_WOH; R⁵ is independently selected from hydrogen and C1-C4 optionally substituted alkyl; R⁶ is independently selected from hydrogen, C1-C30 optionally substituted alkyl, or C2-C30 optionally substituted alkenyl; and w, x, y and z are independently any integer. In some embodiments, the block copolymer comprises a structure of formula lie, and R⁵ is H and R⁶ is C1-C4 optionally substituted alkyl. In some embodiments, the block copolymer comprises two or more block copolymers of formula lie, wherein the block copolymers have properties such as cloud points or molecular weights. In some embodiments, x, y and z are independently any integer from 2 to 100, preferably 4 to 50, more preferably 6 to 40. In some embodiments, w is 1-3, or 1-2, or 1. In some embodiments, the block copolymer has a relatively high molecular weight, such as from about 1000 to 10,000 Daltons (Da), or from 2000 Da to 7000 Da, or from 2000 Da to 4000 Da.

[0034] The block copolymer can be included in the metalworking formulation at any amount suitable to provide desired properties. The amount of the block copolymer can be at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 4.5%, or at least 5%, or at least 5.5%, or at least 6%, or at least 6.5%, or at least 7%, or at least 7.5%, or at least 8%, or at least 9%, or at least 10%, or at least 11%, or at least 12%, or at least 13%, or at least 14%, or at least 15%, or at least 16%, or at least 17%, or at least 18%, or at least 20%; or the amount can be at most 40%, or at most 35%, or at most 30%, or at most 25%, or at most 22%, or at most 20%, or at most 19%, or at most 18%, or at most 17%, or at most 16%, or at most 15%, or at most 14%, or at most

13%, or at most 12%, or at most 11%, or at most 10%, or at most 9.5%, or at most 9%, or at most 8.5%, or at most 8%; it is contemplated that any of these minimums and maximums can be combined to form a range (so long as the minimum is lower than the maximum).

[0035] In some embodiments, the block copolymer comprises at least 10% w/w EO, or at least 15% w/w EO, or at least 20% w/w EO, or at least 25% w/w EO, or at least 30% w/w EO; in some embodiments, the block copolymer comprises at most 70% w/w EO, or at most 60% w/w EO, or at most 50% w/w EO, or at most 40% w/w EO, where the percentage weight is expressed as a percentage of the combination of EO and PO in the copolymer. It is contemplate that any of those minimums and maximums can be combined to form a range. In some embodiments, the polyoxyalkenylene copolymer has end groups derived from secondary alcohols, or that secondary alcohols are used to terminate polymerization of oxyalkenyl monomers.

[0036] Exemplary reverse block copolymers based on EO and PO include PLURONIC 25R2 and 17R2 (available from BASF Corp., NJ), LUMULSE 2017-R and 2025-R (available from Vantage Specialties, Inc., Gurnee, IL), SYNPERONIC PE/25R2 (available from Croda), Chemal BP-3172 and BP-3252 (available from PCC Chemax), and MAKON R-Series (available from Stepan). Such copolymers have high average molecular weights, typically ranging between from 2000 to 4000 Da.

[0037] For the present metalworking formulations, it is desirable to increase their stability, which is generally indicated by higher cloud points of the formulations. Cloud point is the temperature at which cloudiness or turbidity is seen in a liquid. This generally results from separation of a solute from water. The block copolymers contribute significantly to the overall cloud point of the formulation, and in some embodiments, the block copolymers are selected for use in the formulations based the block copolymers’ cloud points. In some embodiments, the present metalworking formulations comprise block copolymers having cloud points in a range of from 25 to 40°C, or from 29 to 35°C.

[0038] In some embodiments, the present metalworking formulations have a shelf life at ambient temperatures of at least about 1 year. In some embodiments, the present formulations exhibit inverse temperature solubility. In some embodiments, the present formulations have a lubricity which increases with increasing temperature, or a coefficient of friction substantially independent of temperature and pressure. In some embodiments, the present formulations comprise an X/Y mixture of first and second reverse block copolymers having different cloud points. For example, the first reverse block copolymer may have a cloud point of about 29°C, the second reverse block copolymer may have a cloud point of about 35°C, and the X/Y ratio is between 1.6:1 and 1 : 1, or is about 1.3: 1. In some embodiments, the present metalworking formulations comprise an X/Y/Z mixture of the first reverse block copolymer, the second reverse block copolymer, and the esterified lubricity additive, and the (X+Y)/Z ratio is between 1.1 : 1 and 2: 1, or is about 1.4: 1, or the X/Y/Z ratio is about 1.3: 1 : 1.7.

[0039] In some embodiments, the present metalworking formulations comprise a desired ratio of block copolymer(s) to esterified lubricity additive(s). For instance, the ratio can be in a range of from 6: 1 to 1 :6, or from 3 : 1 to 1 :3, or from 3 : 1 to 1 :2, or from 3 : 1 to 1 : 1, or from 2:1 to 1: 1.5, or from 2: 1 to 1 : 1.2, or from 2: l to 1: 1, or from 1.5:1 to 1 : 1, or from 1 :4 to 1.3: 1. In some embodiments, the ratio is about 1.5:1, or about 1.4: 1, or about 1.39:1, or about 1.37: 1, or about 1.35:1, or about 1.33:1, or about 1.31 :1, or about 1.28: 1, or about 1.25: 1, or about 1.2: 1. In general, the desired ratio is to be calculated on a weight basis.

[0040] The present metalworking formulations also include an amine, preferably two or more amines. Suitable amines include diglycolamine (DGA), alkanolamines such as triethanolamine (TEA), and N-alkylalkanolamines of various molecular weights (such as

SYNERGEX T, SYNERGEX, SYNERGEX LA, all of which are available from Eastman

Chemical Co., Kingsport, TN).

[0041] In the present formulations, the amine can be a primary, secondary or tertiary amine or an alcohol amine. Examples of primary amines (including alcohol primary amines) include monoethanolamine, monopropanolamine, monoisopropanolamine, 2-amino-l -butanol, 2-amino- 2-methylpropanol, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine and benzylamine. Examples of secondary amines (including alcohol secondary amines) include diethylamine, diisopropylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, di stearylamine, dioleylamine, dibenzylamine, diethanolamine, piperazine, diisopropanolamine, stearylethanolamine, decylethanolamine, hexylpropanolamine, benzilethanolamine, phenylethanolamine and tolylpropanolamine. Examples of tertiary amines (including alcohol tertiary amines) include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, methyldicyclohexylamine, dioleylethanolamine, dilaurylpropanolamine, dioctylethanolamine, dibutylethanolamine, diethylethanolamine, dimethylethanolamine, dihexylpropanolamine, dibutylpropanolamine, oleyl di ethanol amine, stearyldipropanolamine, lauryldiethanolamine, octyldipropanolamine, butyl di ethanol amine, methyldiethanolamine, cyclohexyldiethanolamine, benzyldiethanolamine, phenyldiethanolamine, tolyldipropanolamine, xylyldiethanolamine, triethanolamine, tripropanolamine and triisopropanolamine.

[0042] As noted above, the present metalworking formulations include a corrosion inhibitor formulation which may include an acyl amino acid derivative of formula la, lb or Ic, such as oleyl sarcosine. In some embodiments, the corrosion inhibitor formulations also include a succinic acid derivative, a triazole, a C6-C20 branched carboxylic acid; or a mixture thereof. It has been found that corrosion inhibor formulations comprising an oleyl sarcosine with one or more of a triazole, a sugar alcohol such as sorbitol or xylitol, an imidazoline, and/or a succinic acid derivative unexpectedly provide both good ferrous and aluminum stain resistance. In some embodiments, the corrosion inhibitor formulation consists essentially of ashless components, such as Oleyl sarcosine, imidazoline, and succinic half esters. Ashless components can be advantageous to safeguard the metal from interacting with beverage or decorating inks.

[0043] Suitable succinic acid derivatives include compounds of formulas Va and Vb:

where R⁸ is C1-C30 optionally substituted alkyl or a C2-C30 optionally substituted alkenyl group.

In some embodiments, R⁸ is derived from olefins of 2 to 18 carbon atoms with alpha-olefins being particularly useful. Examples of such olefins include ethylene, propylene, 1 -butene, isobutene, 1-pentene, 2-methyl-l -butene, 3 -methyl- 1 -butene, 1-hexene, 1-heptene, 1-octene, styrene, 1 -nonene, 1 -decene, 1 -undecene, 1 -dodecene, 1 -tridecene, 1 -tetradecene, 1 -pentadecene,

1 -hexadecene, 1 -heptadecene, 1 -octadecene, etc. Alpha olefin fractions such as C12-16 alphaolefins, C14-16 alpha-olefins, C14-18 alpha-olefins, C16-18 alpha-olefins, and others can be used to produce the succinic acid derivative. As used herein, the term “succinic acid derivatives” also emcompass derivatives of succinic anhydride, unless otherwise indicated. Succinic acid derivatives are also described in US Patent Nos. 5,746,837. In some embodiments, the succinic acid derivative is an amidated succinic acid derivative such as Additin RC 4803 (available from Laxness Corp., Pittsburgh, PA) or Rhein Chemie RC 4803 (available from Tri-iso Inc., Cardiff by the Sea, CA). Other corrosion inhibiting components include polyhydric alcohol esters of a succinic acid derivative according to formula Va or Vb, such as a pentaerythritol diester of polyisobutylene-substituted succinic acid.

[0044] Suitable triazoles include tolytriazole, benzotri azole, and triazole salts, such as salts of benzotriazole, tolyl triazole and other triazoles. Brady et al. U.S. Patent No. 6,984,340 discusses triazole derivatives for corrosion inhibiting formulations. Exemplary triazoles include IRGAMET TT 50, available from BASF Corp, or BASF SE.

[0045] In some embodments, the corrosion inhibitor formulation also comprises a carboxylic acid or salt thereof. Examples include caproic/hexanoic acid, enanthic/heptanoic acid, caprylic/octanoic acid, pelargonic/nonionic acid, isononanoic acid, capric/decanoic acid, neodecanoic acid, lauric/dodecanoic acid, stearic/octadecanoic acid, arachidic/eicosanoic acid, palmitic/hexadecanoic acid, erucic acid, oleic acid, arachidonic acid, linoleic acid, linolenic acid, myristic/tetradecanoic acid, behenic/docosanoic acid, alpha-linolenic acid, docosahexaenoic acid, ricinoleic acid, and salts thereof.

[0046] In some embodiments, the formulation comprises a triazole : oleyl sarcosine weight ratio of from 0: 1 to 7: 1, or from 0.35:1 to 2: 1, or from 0.7 : 1 to 1 : 1. In some embodiments, the corrosion inhibitor formulation comprises N-oleyl sarcosine; a water soluble succinic ester with amine; an amidated succinic acid derivative; a sodium salt of tolyl triazole; and neodecanoic acid. In some embodiments, the acyl amino acid derivative is from 0.1% to 5% by weight of the formulation, or from 0.5% to 3% by weight. [0047] The present metalworking formulations can include other components. For instance, metalworking formulations can further comprise a polymeric ashless dispersant. Suitable polymeric ashless dispersants include those derived from the polyesterification of 12- hydroxystearic acid. Oldfield WO 2006/054044 discloses a lubricating composition comprising a polymeric ashless dispersant comprising a polar tail group which comprises a polymeric backbone of 2 to 30 monomeric repeat units, each repeat unit comprising a hydrocarbon chain functionalised by the presence of at least one electronegative element or moiety, the tail group being linked to a polar head group which comprises a polar moiety selected from at least one of acid, ester, amide or alcohol moi eties. Polymeric ashless dispersants such as Hypermer LP1 and Hypermer LP9 are commercially available from Croda Industrial Chemicals,

[0048] The present metalworking formulations can include one or more of a surfactant, a fungicide, a biocide, or a chelating agent. Surfactants for use in the present formulations may include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Examples of anionic surfactants include alkylbenzenesulfonates and alpha-olefin sulfonates. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts. Examples of the amphoteric surfactant include alkylbetaines.

[0049] Nonionic surfactants include alcohol ethoxylates, alkylphenol ethoxylates, fatty acids (such as oleic acid), alkyl polyglycosides, mono-, di- or glyceride esters, (such as diglycerine sesquioleate), acetylated monoglycerides, poly glycerols, polyglycerol esters (such as decaglycerol decaoleate, decaglycerol octaoleate, decaglycerol tetraoleate), mono- or diglyceride esters of citric acid, tartaric acid and lactic acid, sorbitan fatty acid esters (such as sorbitan monostearate, sorbitan monooleate, sorbitan isosterate, sorbitan monolaurate, sorbitan trioleate, sorbitan tristearate, sorbitan sesquioleate, sorbitan monopalmitate, polyol fatty acid esters (such as ethylene glycol distearate, ethylene glycol monostearate, diethylene glycol monostearate, propylene glycol monostearate, propylene glycol monolaurate, polyoxyethylene (1.5) nonylphenol, polyoxyethylene (4) nonylphenol, polyoxyethylene (5) nonylphenol, polyoxyethylene (6) nonylphenol, polyoxyethylene (8) nonylphenol, polyoxyethylene (20) nonylphenol, polyoxyethylene (30) nonylphenol, polyoxyethylene (10) nonylphenol, polyethylene glycol) 200 distearate, polyethylene glycol) 300 dilaurate, poly(ethylene glycol) 400 distearate, polyoxyethylene octylphenol, poly(ethylene glycol) 400 dilaurate, poly(ethylene glycol) 400 monostearate, poly(ethylene glycol) 400 monolaurate, poly(ethylene glycol) 4000 distearate, polyoxyethylene (10) octylphenol, poly(ethylene glycol) 600 monostearate, Polyoxyethylene (14) nonylphenol, polyoxyethylene (24) cholesterol, polyoxyethylene (25) soyasterol, polyethylene glycol) 1000 monooleate, polyoxyethylene (25) propylene glycol monostearate, polyethylene glycol) 1000 monolaurate, polyoxyethylene (70) dinonylphenol), glycerol fatty acid esters (such as glycerol dioleate, glycerol monoleate, glycerol monostearate, glycerol monolaurate, polyoxyethylene (20) glycerol monostearate), sucrose fatty acid esters (such as sucrose distearate, sucrose monolaurate), polyoxyethylene sorbitan fatty acid esters (polysorbates) (such as polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (5) sorbitan monooleate, polyoxyethylene (20) sorbitan monooleate (Tween 80), polyoxyethylene (40) sorbitol hexaoleate, polyoxyethylene (50) sorbitol hexaoleate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monolaurate

(Tween 20), polysorbate 20 NF, EP, JP, polyethylene glycol)-20 sorbitan isostearate, polyethylene glycol) (20) sorbitan trioleate (Crillet 45), polyethylene glycol) (20) sorbitan stearate (Crillet 3 Super, Polysorbate 60), poly(ethylene glycol) (20) sorbitan oleate (Crillet 4 Super, Polysorbate 80), poly(ethylene glycol) (20) sorbitan laurate (Crillet 2 Super, Polysorbate 40)), monoesters (such as polyoxyethylene (4) stearic acid, polyoxyethylene (8) stearic acid, polyoxyethylene (8) lauric acid, polyoxyethylene (40) stearic acid, polyoxyethylene (50) stearic acid), polyethoxylated esters of acyl acids (such as polyoxyethylene (2) octyl alcohol, polyoxyethylene (4) tridecyl alcohol, polyoxyethylene (6) tridecyl alcohol, polyoxyethylene (8) tridecyl alcohol), copolymers of polyethylene oxide and polypropylene oxide, polyoxyethylene fatty ethers (such as polyoxyethylene fatty ethers derived from lauryl, cetyl, stearyl and oleyl alcohols, polyoxyethylene (4) lauryl ether, polyoxyethylene (23) lauryl ether, polyoxyethylene (2) cetyl ether, polyoxyethylene (10) cetyl ether, polyoxyethylene (20) cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (10) stearyl ether, polyoxyethylene (20) stearyl ether, polyoxyethylene (2) oleyl ether, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, polyoxyethylene (21) stearyl ether, polyoxyethylene (12) lauryl ether), fatty amides (such as N,N, -Dimethylstearamide), Polyethylene glycol ether of linear alcohol, polyoxyethylene (15) tall oil fatty acids (ester), acetylated sucrose diesters, isopropyl ester of lanolin fatty acids, polyoxyethylene sorbitol beeswax derivative, Polyoxypropylene/Polyoxyethylene condensate, sodium oleate, polyoxyethylene (20) castor oil (ether, ester), glycerol oleate & propylene glycol.

[0050] In some embodiments, the formulation comprises nonionic surfactants selected from alkylphenol ethoxylates, linear alcohol ethoxylates, polyoxyethylene glycol sorbitan esters, polyoxyethylene glycol sorbitol esters, and mixtures thereof. In some embodiments, the fomrpulation comprises at least one alkylphenol ethoxylate or linear alcohol ethoxylate, and at least one polyoxyethylene glycol sorbitan ester or polyoxyethylene glycol sorbitol ester, such as polyoxyethylene glycol sorbitan hexaoleate or polyoxyethylene sorbitol hexaoleate.

[0051] In some embodiments, the present metalworking formulations include an ester oil such as neopentyl glycol dioleate, trimethylolpropane trioleate, pentaerythritol tetraoleate, propylene glycol dioleate, ricinoleic acid condensate, and methyl ester of soybean oil, canola oil, jatropha oil or palm oil, and combinations thereof. Suitable amounts of an ester oil include at least 0.5%, or at least 1%, or at least 2%, or at least 3%, or at least 4% or at least 5%, or at least 6%, or at least 7%, or at least 8%; or at most 20%, or at most 18%, or at most 15%, or at most 12%, or at most 10%, or at least 9%; the foregoing percentages can be combined to form a range. [0052] In some embodiments, the present formulations are substantially free of one or more components which have been frequently used in prior metalworking fluids. For instance, some embodiments are substantially free of a coupler such as dipropylene glycol monobutyl ether. In some embodiments, the present formulations are substantially free of phosphoric acid derivatives such as phosphate esters. In some embodiments, the present formulations are substantially free of boric acid derivates such as borate esters. In some embodiments, the present formulations are substantially free of corrosion inhibiting components that are film-formers on metal surfaces.

[0053] In some embodiments, the present metalworking formulations reduce or avoid fatty acid components which are used in commercial coolant fluids. Fatty acid components tend to yield aluminum soaps either in the cupper, bodymaker or during washing in an acidic can washer. Formation of aluminum soaps leads to short filter cycle time for filters used for cleaning and recycling coolant fluids. It also requires more frequent washer maintenance. In some embodiments, the present metalworking formulations are substantially free of fatty acid components that form aluminum soaps; alternatively the formulations have less than 5%, or less than 3%, or less than 1% of such components.

[0054] The present metalworking formulations can be used as-is or neat, or they may be diluted in another fluid such as water, an organic solvent, a hydrocarbon liquid or mixtures thereof to form a diluted composition. For instance, the present metalworking formulations may be provided in a diluted metalworking composition in which the water or other diluent is from 0.1% to 99.9% of the total composition, alternatively from 1% to 99%, or from 10% to 98%, or from 40% to 97%, or from 80% to 95% of the total composition. For example, diluted metalworking compositions may contain 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14%, or 15% of the present metalworking formulations, one or more other components, and water and/or another diluent; it is also contemplated that any of those percentages can be combined to form a desirable range. In some embodiments, a diluted metalworking composition consists essentially of an amount (such as one of the foregoing percentages) of the present metalworking formulations and water and/or another diluent. In some embodiments, a diluted metalworking composition consists essentially of an amount (such as one of the foregoing percentages) of the present metalworking formulations, a hydrocarbon-based lubricant, and water and/or another diluent. In some embodiments, the diluted composition comprises 5% w/w or less of a hydrocarbon-based lubricant, or 4% or less, or 3% or less, or 2% or less, or 1% or less.

[0055] In some embodiments, the present metalworking formulations repels one or more gear oil components, such as a high molecular weight hydrocarbon component, or an organosulfur and/or phosphate compounds, or other inorganic compounds as extreme pressure (EP) additives or antiwear additives. In some embodiments, present metalworking formulations substantially repels high viscosity hydrocarbon lubricants.

[0056] It is to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. The defined terms are in addition to the technical and scientific meanings of the defined terms as commonly understood and accepted in the technical field of the present teachings.

[0057] As used in the specification and appended claims, and in addition to their ordinary meanings, the terms "substantial" or "substantially" mean to within acceptable limits or degree to one having ordinary skill in the art. For example, "substantially free" of a compound means that one skilled in the art considers the amount of the compound present is negligible and/or undetectable.

[0058] As used in the specification and the appended claims and in addition to its ordinary meaning, the terms "approximately" and "about" mean to within an acceptable limit or amount to one having ordinary skill in the art. The term "about" generally refers to plus or minus 15% of the indicated number. For example, "about 10" may indicate a range of 8.5 to 11.5. For example, "approximately the same" means that one of ordinary skill in the art considers the items being compared to be the same. Whenever a value is recited in the present disclosure, it should be understood that an approximate value is also disclosed; for example, where a value of 5 or 10 is disclosed, it should be understood that “about 5” and “about 10” are also disclosed.

[0059] In the present disclosure, numeric ranges are inclusive of the numbers defining the range. It should be recognized that chemical structures and formula may be elongated or enlarged for illustrative purposes. [0060] Whenever a range of the number of atoms in a structure is indicated (e.g., a C1-C30 alkyl, C2-C30 alkenyl, etc.), it is specifically contemplated that the substituent can be described by any of the carbon atoms in the sub-range or by any individual number of carbon atoms falling within the indicated range. By way of example, a description of the group such as an alkyl group using the recitation of a range of 1-30 carbon atoms (e.g., C1-C30), encompasses and specifically describes an alkyl group having any of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30 carbon atoms, as appropriate, as well as any subrange thereof (e.g., 2-8 carbon atoms, 2-12 carbon atoms, 3-16 carbon atoms, as appropriate).

[0061] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those working in the fields to which this disclosure pertain. [0062] As disclosed herein, sets and ranges of values are provided. For a set of values, it should be understood that any two values of the set can be combined to form a range. It should also be understood that each intervening value in a set or range, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the present disclosure. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the present disclosure, subject to any specifically excluded limit in the stated range.

[0063] When a percentage is provided for the amount of a component in a formulation, it refers to the weight of the component divided by the weight of the total composition (w/w), unless indicated otherwise. [0064] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present teachings, some exemplary methods and materials are now described.

[0065] All patents and publications referred to herein are expressly incorporated by reference.

[0066] As used in the specification and appended claims, the terms "a," "an," and "the" include both singular and plural referents, unless the context clearly dictates otherwise. Thus, for example, "a component" includes one component and plural components.

[0067] The term “substituted” in reference to alkyl, alkenyl or other chemical group, for example, “substituted alkyl”, means alkyl or other group in which one or more hydrogen atoms are each independently replaced with a non-hydrogen substituent. Typical substituents include, but are not limited to, — X, — R, — O-, =0, — OR, — SR, — S-, — NR2, — N^Rs, =NR, — CX3, — CN, — OCN, — SCN, — N=C=O, — NCS, —NO, — NO2, =N₂, — N3, — NHC(=O)R, — NHS(=O)₂R, — C(=O)R, — C(=0)NRR— S(=O)₂O- — S(=O)₂OH, — S(=O)₂R, — OS(=O)₂OR, — S(=O)₂NR, — S(=O)R, — OP(=O)(OR)2, — P(=O)(OR)2, — P(=O)(O-)2, — P(=O)(OH)₂, — P(O)(OR)(O-), — C(=O)R, — C(=O)OR, — C(=O)X, — C(S)R, — C(O)OR, — C(O)O- — C(S)OR, — C(O)SR, — C(S)SR, — C(O)NRR, — C(S)NRR, — C(=NR)NRR, where each X is independently a halogen: F, Cl, Br, or I; and each R is independently H, alkyl, aryl, arylalkyl, a heterocycle, or a protecting group. Alkylene groups may also be similarly substituted. When the number of carbon atoms is designated for a substituted group, the number of carbon atoms refers to the group, not the substituent (unless otherwise indicated). For example, a Ci-4 substituted alkyl refers to a Ci-4 alkyl, which can be substituted with groups having more than, e.g., 4 carbon atoms.

[0068] The term "alkyl" refers to a straight-chain or branched hydrocarbon. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, //-butyl, ec-butyl, isobutyl, tert-butyl, pentyl, isoamyl, hexyl, and the like. Alkyl groups may be unsubstituted or substituted, as defined above.

[0069] The term "alkenyl" refers to a straight or branched hydrocarbon, having one or more carbon-carbon double bonds. Nonlimiting examples of alkenyl groups include ethenyl, 1- propenyl, 2-propenyl (allyl), zso-propenyl, 2-methyl-l-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups may be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0070] “Heteroalkyl” and “heteroalkenyl” refer respectively to an alkyl group and an alkenyl group in which one or more carbon atoms have been replaced with a heteroatom, such as, O, N, or S. Any carbons within the alkyl group or the alkenyl group can be replaced independently with a heteroatom (O, N, or S), meaning the first carbon, the terminal carbon or an internal carbon. For example, if the carbon atom of an alkyl group which is attached to the parent molecule is replaced with a heteroatom (e.g., O, N, or S) the resulting heteroalkyl groups may be referred to, respectively, an alkoxy group (e.g., — OCH3, etc.), an amine alkyl (e.g., — NHCHs, — N(CHS)2, etc.), or a thioalkyl group (e.g., — SCH3). If a non-terminal carbon atom of the alkyl group which is not attached to the parent molecule is replaced with a heteroatom (e.g., O, N, or S) the resulting heteroalkyl groups may be referred to, respectively, an alkyl ether (e.g., — CH2CH2— O— CH3, etc.), an alkyl amine (e.g., — CH2NHCH3, — CH₂N(CH₃)2, etc.), or a thioalkyl ether (e.g., — CH2 — S — CH3). If a terminal carbon atom of the alkyl group is replaced with a heteroatom (e.g., 0, N, or S), the resulting heteroalkyl groups may be referred to, respectively, a hydroxyalkyl group (e.g., — CH2CH2 — OH), an aminoalkyl group (e.g., — CH2NH2), or an alkyl thiol group (e.g., — CH2CH2 — SH). A heteroalkyl group or a heteroalkenyl group can have, for example, 1 to 24 carbon atoms. A Ci-Ce heteroalkyl group means a heteroalkyl group having 1 to 6 carbon atoms. A “substituted heteroalkyl” or a “substituted heteroalkenyl” means a heteroalkyl or a heteroalkenyl as defined herein in which one or more hydrogen atom has been replaced with a non-hydrogen substituent as defined in the “substituted” definition.

[0071] The term "aryl" refers to an unsubstituted or substituted aromatic carbocyclic substituent, as commonly understood in the art, such as phenyl, naphthyl, anthracyl, indanyl, and the like. Aryl groups may be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0072] The term "heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered aromatic ring system. Non-limiting examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, l,3,4-oxadiazol-2-yl, l,2,4-oxadiazol-2-yl, 5-methyl-l,3,4-oxadiazole, 3-methyl-l,2,4-oxadiazole, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, quinazolinyl, and the like. Heteroaryl groups may be unsubstituted or substituted, as defined above.

[0073] The term "heterocycle" or "heterocyclyl" refers to a monocyclic, bicyclic, or tricyclic moiety containing 1 to 4 heteroatoms selected from O, N, and S. Heterocyclyl groups optionally contain one or more double bonds. Heterocyclyl groups include, but are not limited to, azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl, indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, and benzoxazinyl. Heterocyclic groups may be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0074] The term "carbonyl" refers to a substituent comprising a carbon double bonded to an oxygen. Examples of such substituents include aldehydes, ketones, carboxylic acids, esters, amides, carbonates, and carbamates. Carbonyl groups may be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0075] The term "amino" refers to any nitrogen-containing moiety. Non-limiting examples of the amino group are NH2- (primary), R⁷HN- (secondary), and R⁷2N(tertiary) where R⁷ is alkyl, alkenyl, alkynyl, aryl, heterocyclic, or heteroaiyl. R⁷HN- and R⁷2N groups may be unsubstituted or substituted, as defined above.

[0076] "Halogen" or "halo" refers to fluorine, chlorine, bromine, and iodine.

[0077] Before the various embodiments are described, it is to be understood that the teachings of this disclosure are not limited to the particular examples described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present teachings will be limited only by the appended claims.

EXAMPLES

[0078] In some of the following examples, metalworking fluids are evaluated by Microtap torque testing. Such testing is commonly used to determine a metalworking fluid’s ability to lubricate a metal surface. In Microtap testing, a metal bar with predrilled holes is fastened to a vice. The tap and the metal bar are coated in the metalworking fluid to be tested. The tap rotates to tap out the pre-drilled hole. The force needed to tap the hole is measured by a computer and is reported as torque in newton-meters (N-m). Alternatively, measured values can be normalized with respect to each other, such that the results of a given experiment are reported as a percentage versus a standard (rather than in N-m). In the following examples, Microtap torque testing was conducted with the following equipment and parameters.

[0079] The testing equipment was a Tauro 120 T, with TauroLink software. The test material was 6061 T6 Aluminum, provided as a test bar measuring 14” X 2” X 'A” with reamed holes. A YMW 388521 forming tap (M6, HSS Nitride surface treated) was used, and the speed was set at 800 RPM, with Surface speed - 49.4 fpm, Surface Speed - 15.05 mpm.

[0080] In the following examples, the role or function of various components may be indicated as an aid to understanding the examples and the inventive formulations. It should be noted, however, that a given component may or may not perform a given role or function in some embodiments, and that a component need not be limited to a single role or function.

[0081] In the following examples, various compositions may have concentrations of various components, with water as the “balance” of the composition. It should be noted that this indicates a sufficient amount of water is included to yield the recited concentrations, which may include more or less water as components are increased, decreased, added or omitted.

EXAMPLE 1

[0082] In this example, an embodiment of the inventive metalworking formulations was prepared. Table 1 shows the components of the Example 1. The formulation of Example 1 is suitable for various uses, including as a coolant for a bodymaker in manufacture of thin-walled metal containers. Table 1

EXAMPLE 1A

[0083] 30 g of Example 1 is combined with 970 g water to form a diluted metalworking composition comprising 3% of the metalworking formulation of Example 1. The composition of Example 1A is suitable for various uses, including as a coolant for a bodymaker in manufacture of thin-walled metal containers.

EXAMPLE 2

[0084] This example provides another embodiment of the inventive metalworking formulations. Table 2 shows the components of the formulation. The formulation of Example 2 is suitable for various uses, including as a coolant for a bodymaker in manufacture of thin-walled metal containers. Table 2

[0085] Example 2 contains a more complex corrosion inhibitor formulation. It is believed that the multiple components of the corrosion inhibitor formulation cooperatively and unexpected reduce corrosion and residue on metal surfaces. EXAMPLE 2A

[0086] 30 g of Example 2 is combined with 970 g water to form a diluted metalworking composition comprising 3% of the metalworking formulation of Example 2. The composition of Example 2A is suitable for various uses, including as a coolant for a bodymaker in manufacture of thin-walled metal containers.

EXAMPLE 3

[0087] In this example, an embodiment of the inventive metalworking formulations was compared to a commercial metalworking fluid used as a coolant (Henkel 540B). Table 3 shows the components of the commercial formulation (to the extent known).

Table 3

[0088] Microtap torque testing was used to compare the lubricity of Example 1 to the commercial formulation, and the results are shown in FIG. 1. The formulations were applied without dilution to the Microtap testing equipment, and the torque was measured. The torque for the Example 1 formulation was 1.423 N-m, whereas the torque for the commercial product was 2.501 N-m, indicating significantly better lubricity with Example 1.

EXAMPLE 4 [0089] In this example, a multiday-experiment was conducted to evaluate performance of Example 1 as a metalworking fluid for aluminum can manufacturing (more particularly, as a coolant used with a bodymaker). The formulation of Example 1 was added to the coolant tank of a bodymaker for manufacturing a thin-walled aluminum beverage can, such that the diluted metalworking composition in the tank comprised about 6 wt. %. Example 1 and water as the remainder. On Days 2-10 of the experiment, the concentration of Example 1 was raised to 7% wt. The equipment was operated, and a portion of retained metalworking fluid was collected for Microtap analysis.

[0090] FIG. 2 shows the results of the Microtap testing performed on each of Days 1 to 10. Without intending to be bound by theory, it is believed that the lower torque values on Days 2-10 are primarily attributable to equilibration of equipment operation rather than concentration of the metalworking formulation. Nevertheless, the torque value of 1.609 N-m indicates very good lubricity from the coolant composition, and the torque values of 1.181 to 1.309 indicate excellent lubricity.

EXAMPLE 5

[0091] In this example, performance of the metalworking formulation of Example 2 was evaluated over the course of several months. Beginning on Day 1, the metalworking formulation was added to a coolant tank for the bodymaker of an aluminum can manufacturing line. The coolant tank has a capacity of 7000 gallons, such that the diluted metalworking composition in the tank comprised about 3 wt. %. A cupping lubricant (BONDERITE L-FM SNL-3 Acheson Cupper Lubricant, from Henkel Corp., Madison Heights, MI), was also added to the coolant tank to provide a concentration of about 1.0 wt. %. Table 4 sets forth general information about the components of the SNL-3 cupping lubricant. Table 4

[0092] On Day 7, the concentration of the Example 2 formulation in the coolant tank was increased to about 6 wt. %, and about 50 gallons of the cupping lubricant were added to the coolant tank. The can manufacturing equipment was operated, and a portion of retained metalworking fluid was collected for Microtap analysis.

[0093] FIG. 3 shows the results of the Microtap analysis in N-m over several months.

Without intending to be bound by theory, it is believed that the torque values decreased over an initial equilibration period of approximately one month. After such equilibration, the metalworking composition had lubricity values below 1.5, ranging from about 1.151 to 1.444.

EXAMPLE 6

[0094] In this example, performance of the metalworking formulations of Examples 1 and 2 in large scale manufacturing equipment was compared to a laboratory prepared sample of Example 2. The diluted metalworking compositions comprised about 6 wt. % of those metalworking formulations and about 1 wt. % of a cupping lubricant.

[0095] Example 6A employed the metalworking formulation of Example 1, Examples 6B, 6C and 6E employed the formulation of Example 2, and Example 6D employed a mixture of Examples 1 and 2. Examples 6A, 6B, and 6C were samples from large preparations of coolant fluids. Example 6D was combination of Example 6A and 6B samples. Example 6E was a small scale preparation in a laboratory 100 mis.) Examples 6A to 6E were evaluated by Microtap testing neat (without dilution).

[0096] FIG. 4 shows the results of the Microtap analysis in N-m. The torque values measured for each of the examples were consistent with each other, and they demonstrated excellent lubricity. The larger scale preparations (Exs. 6A to 6D) were consistent with the laboratory scale preparation.

[0097] This example demonstrated that a laboratory prepared coolant fluid matched large scale preparations; with addition of 1 wt.% cupping lube, they yielded similar Microtap torque values. These Microtap values showed close agreement with long term evaluation of a coolant fluid (see data in FIG. 3 over 200 + days). It is contemplated that the Microtap torque test can provide valuable insight as to the lubricity of a neat metalworking formulation for quality control purposes and likewise could be used to track in-use coolant lubricity, thereby providing a means of troubleshooting.

EXAMPLE 7

[0098] In this example, performance of the Henkel 540B coolant fluid was examined when used on different lines of aluminum can manufacturing equipment comprising a bodymaker. The examination was done to establish a benchmark for comparison to inventive coolant fluids. The diluted metalworking compositions (comparative Examples C7A to C7H) comprised about 3 wt. % of Henkel 540B and about 1 wt. % of a cupping lubricant. Exs. C7A to C7C were used on a can manufacturing line at periods several months apart. Ex. C7D and C7E were used on another line, and the results are about four weeks apart. Examples C7F to C7I were used on different large-scale manufacturing lines, and Example 7J was used in a pilot line. Example 7J included

Example 1 in the coolant fluid. [0099] FIG. 5 shows the torque values in N-m measured for each of the examples. The torque values were higher than those in FIG. 4, which is expected in view of the lower concentration of the metalworking formulation.

EXAMPLE 8

[00100] In this example, performance of various metalworking compositions comprising the formulation of Example 2 was examined and compared to a commercially available metalworking fluids. The diluted metalworking compositions comprised various percentages of metalworking formulations similar to that of Example 2, except they did not include the water soluble succinic ester with amine. Most of the diluted metalworking compositions also comprised a cupping lubricant (Henkel 5 IE or Henkel SNL-E). Some examples included an ester oil (neopentyl glycol dioleate). The compositions were employed as a coolant for the bodymaker of a large-scale aluminum can manufacturing line. The Comparative Example C8 comprised 4% Henkel 540 B metalworking formulation, 1.8% Henkel 5 IE cupping lubricant, and about 1% tramp oil. Such an amount of tramp oil in a coolant fluid for metalworking can be beneficial in providing higher lubricity, but tramp oil is disadvantageous in being more difficult to reliably clean off surfaces. The compositions of the experimental compositions is set forth in Table 5:

Table 5

[00101] FIG. 6 shows the torque values in N-m measured for each of the examples. Overall, the torque values in FIG. 6 are consistent with each other, and demonstrate excellent lubricity.

Furthermore, with the block copolymer and esterified trimer acid at a ratio of 1.37: 1, the addition of more cupping lubricant and the addition of tramp oil shown very little or no improvement in lubricity, especially with Example 2 present in amounts at 5 wt.% and above. With a 1 : 1 ratio of block copolymer and esterified trimer acid, the formulation of Example 2 provides consistent lubricity at amonts above 3 wt.%. Lubricity becomes constant and begins to enter full hydrodynamic lubrication.

[00102] With the addition of a neopentyl ester oil to Example 2 at 6 wt.%, Example 8G achieve a Microtap torque value of 1.6 N-m. It is surprising that such lubricity could be obtained without the addition of cupping lubricant. The 1.6 N-m value is similar to the lubricity observed with commercial coolant fluids with 1 wt.% cupping lubricant. With a cupping lubricant included in the metalworking composition, Microtap torque values of 1.0 to 1.1 N-m are obtained (See Examples 8H and 81).

[00103] Thus, the present formulations make it practical to apply a coolant fluid to a bodymaker with oil or hydrocarbon lubricant. The reduction or removal of oil makes cleaning of workpieces such as cans and manufacturing equipment significantly easier. EXAMPLE 9

[00104] In this example, a metalworking formulation having a lower ratio of block copolymer to lubricity additive was examined. The Example 9 metalworking formulation was the same as the formulation of Example 2, except that the block copolymer : lubricity additive ratio was 1 : 1 (rather than 1.37: 1 as in Example 2). The metalworking compositions contained coolant and cupping lubricant as set forth in Table 6:

Table 6

[00105] The metalworking compositions of Examples 9A to 91 were subjected to Microtap testing, and the results are shown in FIG. 7. It was observed that compositions comprising the Example 9 formulation exhibited its best lubricity at an amount of 3 wt.% with 1 wt.% of the cupping lubricant. It was unexpectedly found that compositions comprising 4 wt. % of the Example 9 formulation with 1 wt.% of the cupping lubricant yielded higher torque values than with 3 wt.% of that formulation. Without intending to be bound by theory, it is believed that at concentrations above 3 wt.% of Example 9, or concentrations at 4% or higher, viscous drag reduces lubricity.

[00106] FIG. 7 also illustrates Microtap torque values vs concentration of the various metalworking fluids. Such information could be used to select a desired lubricity for an intended application.

EXAMPLE 10

[00107] In this example, metalworking formulations having different components were evaluated. The metalworking formulations of Examples 10A, 10B and 10C, had the same components as the formulation of Example 2, with the following exceptions. Example 10A did not include the water soluble succinic ester with amine (XP-21), but included 1.5 wt. % KETIENLUBE 445 (“KL445”), a polymeric ester with ethoxylated side chains (available from Italmatch Chemicals, Genova, Italy). Example 10B did not include XP-21, but included 5 wt. % KL445. Example 10C included a higher amount (5 wt. %) of the corrosion inhibitor XP-21. Formulations 2, 10A, 10B and 10C were added at a concentration of 6 wt. % to form diluted coolant compositions, which also included 1 wt . % cupping lubricant. The diluted coolant compositions were evaluated by Microtap testing, and the results are shown in FIG. 8.

[00108] The water soluble succinic ester is believed to increase hydrodynamic lubrication and is not likely to be removed with tramp oil. It was theorized that a polymeric ester with ethoxylated side chains might provide similar performance, and it is available in Europe. It also can be added directly to the concentrated metalworking formulation with only mixing required. [00109] FIG. 8 demonstrates that the polymeric ester with ethoxylated side chains is a successful replacement for the water soluble succinic ester with amine, providing equal or better lubricity, with torque values of 1.289 N-m and 1.344 N-m, for Examples 10A and 10B, respectively.

EXAMPLE 11

[00110] In this example, additional embodiments of the inventive metalworking formulations were evaluated. The metalworking formulations of Examples 11A, 1 IB and 11C had the same components as the formulation of Example 2, with the following exceptions. Example 11 A replaced the water dispersible ETA with AltaLUB 5300, which is a partial or half-ester of a compound derived from the Diels-Alder reaction of a conjugated fatty acid and an acid precursor dienophile. Example 1 IB replaced the water dispersible ETA with about 14 wt. % TAS XP-48, and the amount of block copolymer was reduced by about 2 wt. %. XP-48 is an reaction product of a polyalkanoic or polyalkenoic acid derived from hydroxyfatty acids and a block copolymer comprising polyoxyalkylene blocks. Example 1 IB also replaced Rhein Chemie RC 4803 with octyl succinic anhydride. Example 11C replaced the water dispersible ETA with TAS XP-48, and also replaced Rhein Chemie RC 4803 with 3-4 wt. % octyl succinic anhydride. Examples 11 A, 1 IB and 11C were added to form diluted coolant compositions, and evaluated by Microtap testing. The results are shown in FIG. 9. Rather than showing results in N-m, the results are normalized versus a diluted coolant compositions comprising the formulation of Example 1.

[00111] Example 11A displayed good lubricity though it was not as lubricious as Example 1. Examples 1 IB and 11C displayed excellent lubricity, and demonstrated that the present metalworking formulations can employ an esterified lubricity additive other than a water dispersible ETA. Examples 1 IB and 11C also demonstrate that octyl succinic anhydride is a suitable alternative to an amidated succinic acid derivative, and that a reaction product of polyalkenoic/polyalkenoic acid and a block copolymer (such as XP-48) is a suitable alternative to water dispersible ETAs and/or surfactants.

EXAMPLE 12

[00112] In this example, a practical advantage of the present metalworking formulations is demonstrated in the form of reduced filter blockage and extended filter life. Filters are employed as coolant fluid employed on a bodymaker is collected and returned to a coolant tank. The used coolant fluid is passed through a filter, such as a Cuno filter, before being used again as coolant on the bodymaker. Filter operation can be monitored by measuring the pressure drop across the filter, with a higher pressure indicating a blocked filter that may need replacement.

[00113] When a coolant composition comprising the formulation of Example 2 was used, it was observed that the filter’s effective life was significantly increased, and filter replacement was required far less frequently. FIG. 10 is a graph showing the pressure drop measured over extended periods when using the coolant composition. As can be seen, the periods over which the filters were effective extended for 40 days or longer, compared to periods as short as 75 to 90 hours which have been experienced with commercial coolant fluids.

[00114] Without intending to be bound by theory, it is believed that the superior filter performance of the present formulations is attributable to being substantially free of phosphoric acid derivates, boric acid derivates and other corrosion inhibiting components that are filmformers.

[00115] As a further illustration of the practical advantages of the present formulations, FIG.

11 shows photographs of Cuno filters used for cleaning coolant fluids which have been used on a bodymaker. The photograph on the left is from equipment where a commercial coolant fluid was applied to the bodymaker and the manufacturing line was run for 6 days. As can be seen, significant sludge built up on the filter, and the pressure drop across the filter was 25 psi, indicating that the filter should be changed in the near future. The photograph on the right is from equipment where a coolant fluid comprising Example 2 was applied to the bodymaker and run for about one month. Little buildup is seen on the filter, and the pressure drop had not significantly increased since installation of the filter.

[00116] FIG. 12 shows photographs of a drip pan beneath conveyors in an aluminum can manufacturing line. The drip pan collects fluids from the bodymaker. The photo on the left is from equipment where a coolant fluid comprising Example 2 was applied to the bodymaker; the photo on the right is from equipment where a commercial coolant fluid was applied to the bodymaker. The photographs show the difference between the coolant fluids in sludge buildup, in that no sludge was observed from the Example 2 composition after 30 days of use. In contrast, the commercial coolant fluid significant sludge formation.

Claims

CLAIMS What is claimed is:

1. A metalworking formulation comprising: an esterified lubricity additive; a block copolymer; an amine; and a corrosion inhibitor formulation, wherein the corrosion inhibitor formulation comprises an acyl amino acid derivative of formula la, lb or Ic:

R¹-(CO)-N(R²)— (CH₂)n-CO₂X (la)

[R¹-(CO)-N(R²)— (CH₂)n-CO₂]m-Z-(OH)p (Ic) where:

R¹ is Ce-Cso optionally substituted alkyl or C6-C30 optionally substituted alkenyl, and

R² is hydrogen or C1-C4 optionally substituted alkyl;

X is hydrogen, C1-C30 optionally substituted alkyl, or C₂-Cso optionally substituted alkenyl;

Y is an alkali metal or an alkaline earth metal;

Z is a residue remaining after removal of a hydroxyl group from a polyhydric alcohol; m is an integer of 1 or greater, which is 1 when Y is an alkali metal and 2 when Y is an alkaline earth metal; p is an integer of zero or greater; n is an integer of 1 to 4, and

43 m+p is the valency of Z.

2. The metalworking formulation of claim 1, wherein the corrosion inhibitor formulation further comprises a succinic acid derivative, a triazole, a C6-C20 branched carboxylic acid, a sugar alcohol, an imidazoline, or a mixture thereof.'

3. The metalworking formulation of claim 2, wherein the formulation comprises a triazole : oleyl sarcosine weight ratio of from 0: 1 to 7:1.

4. The metalworking formulation of claim 1, wherein the corrosion inhibitor formulation comprises:

N-oleyl sarcosine; a water soluble succinic ester; an amidated succinic acid derivative; a sodium salt of tolyl triazole; and neodecanoic acid.

5. The metalworking formulation of claim 1, wherein the acyl amino acid derivative is from 0.1% to 5% by weight of the formulation.

6. The metalworking formulation of claim 1, wherein the acyl amino acid derivative is N-oleyl sarcosine.

44 The metalworking formulation of claim 1, wherein the formulation does not significantly stain aluminum.

8. The metalworking formulation of claim 7, wherein the formulation is substantially free of phosphoric acid derivatives.

9. The metalworking formulation of claim 7, wherein the formulation is substantially free of boric acid derivates.

10. The metalworking formulation of claim 7, wherein the formulation is substantially free of corrosion inhibiting components that are film-formers on metal surfaces.

11. The metalworking formulation of claim 1, wherein the esterified lubricity additive is a water dispersible esterified dimer or trimer acid, wherein the dimer or trimer acid is the esterification product of: (1) an acid component comprising a dimer acid, a trimer acid, or a mixture thereof; and (2) an alcohol component comprising an alkylalkoxy alcohol, optionally in combination with an alkyl alcohol.

12. The metalworking formulation of claim 1, wherein the esterified lubricity additive is an esterification reaction product selected from the group consisting of: (a) a polyalkanoic or polyalkenoic acid derived from hydroxyfatty acids and a block copolymer selected from the group consisting of polyoxyethylene-polyoxypropylene and a reverse block copolymer of polyoxypropylene-polyoxyethylene-polyoxypropylene; (b) the reaction product of

(a) with a maleic acid or anhydride; and (c) mixtures thereof

13. The metalworking formulation of claim 1, wherein the esterified lubricity additive is a partial or half-ester of a compound derived from the Diels-Alder reaction of a conjugated fatty acid and an acid precursor dienophile.

14. The metalworking formulation of claim 1 comprising the esterified lubricity additive and the block copolymer at a ratio of from 3 : 1 to 1 :3 w/w.

15. The metalworking formulation of claim 1 wherein the block copolymer comprises a structure represented by formula (Ila), (lib) or (lie):

R³-(EO)x-(PO)_y-R⁴ (Ila)

R³-(EO)x-(PO)_y-(EO)_z -R⁴ (lib)

R³-(PO)x-(EO)y-(PO)z -R⁴ (Re) where w, x, y and z are independently any integer;

R³ and R⁴ are independently selected from -H, -OH, -(CR⁵R⁶)_WH, or -(CR⁵R⁶)_WOH;

R⁵ is independently selected from hydrogen and C1-C4 optionally substituted alkyl, and

R⁶ is independently selected from hydrogen, C1-C30 optionally substituted alkyl, or C2- C30 optionally substituted alkenyl.

16. The formulation of claim 15, wherein the block copolymer comprises a structure of formula lie, and R³ is H and R⁶is C1-C4 optionally substituted alkyl.

17. The metalworking formulation of claim 1 wherein the block copolymer comprises two or more block copolymers of formula lie.

18. The metalworking formulation of claim 1, wherein the composition comprises: from about 3.25% to about 13.5% of the esterified lubricity additive; from about 4% to about 19.5% of the block copolymer; from about 1% to about 5% of a polymeric surfactant antifoaming agent; from about 0.1% to about 2% of N-oleyl sarcosine; from about 0.1% to about 2% of a water soluble succinic ester; from about 0.1% to about 2% of an amidated succinic acid derivative; from about 0.1% to about 2% of a triazole; and from about 2% to about 8% of carboxylic acid.

19. The metalworking formulation of claim 1, wherein the formulation is stable at temperatures between 0°C and 45°C.

20. The metalworking formulation of claim 1, wherein the formulation has a cloud point temperature of at least about 45°C.

21. The metalworking formulation of claim 1, wherein the formulation repels one or more gear oil components.

22. The metalworking formulation of claim 1, wherein the formulation has a shelf life at ambient temperatures of at least about 1 year.

23. The metalworking formulation of claim 1, wherein the formulation exhibits inverse temperature solubility.

24. The metalworking formulation of claim 1, wherein the formulation has a lubricity which increases with increasing temperature, or a coefficient of friction substantially independent of temperature and pressure.

25. The metalworking formulation of claim 1, wherein the formulation comprises an X/Y mixture of first and second reverse block copolymers having different cloud points.

26. The formulation of claim 25, wherein the first reverse block copolymer has a cloud point of about 29°C, the second reverse block copolymer has a cloud point of about 35°C, and the X/Y ratio is between 1.6: 1 and 1 :1.

27. The metalworking formulation of claim 25, wherein the formulation comprises an X/Y/Z mixture of the first reverse block copolymer, the second reverse block copolymer, and / the esterified lubricity additive, and the (X+Y)/Z ratio is between 1.1: 1 and 2:1.

28. The metalworking formulation of claim 1, wherein the formulation is ashless or consists essentially of ashless components.

48

29. The metalworking formulation of claim 1, wherein the formulation degrades to low molecular weight degradation products.

30. A diluted metalworking composition comprising any of the foregoing metalworking formulations in an amount effective to provide lubricity, and a diluent.

31. The composition of claim 30, wherein the diluent is water, and the amount of the formulation is from 1% to 10% w/w.

32. The diluted composition of claim 30, further comprising 3% w/w or less of a hydrocarbon-based lubricant.

33. A corrosion inhibitor formulation for inhibiting corrosion of iron and aluminum, wherein the formulation comprises:

(a) an acyl amino acid derivative of formula la, lb or Ic:

R¹-(CO)-N(R²)— (CH₂)_n-CO2X (la)

[R¹-(CO)-N(R²)— (CH2)n-CO2]mY (lb)

[R¹-(CO)-N(R²)— (CH₂)n-CO2]m-Z-(OH)_P (Ic) wherein:

R¹ is C6-C30 optionally substituted alkyl or C6-C30 optionally substituted alkenyl, and

R² is hydrogen or C1-C4 alkyl;

49 X is hydrogen, C1-C30 optionally substituted alkyl, or C1-C30 optionally substituted alkenyl;

Y is an alkali metal or an alkaline earth metal;

Z is a residue remaining after removal of a hydroxyl group from a divalent or greater poly hydric alcohol; m is an integer of 1 or greater, which is 1 when Y is an alkali metal and 2 when Y is an alkaline earth metal; p is an integer of zero or greater; n is an integer of 1 to 4, and m+p is the valency of Z;

(b) a water soluble succinic ester and/ or an amidated succinic acid derivative; and

(c) a triazole.

34. The corrosion inhibitor formulation of claim 33, wherein the formulation provides ferrous and aluminum corrosion resistance.

35. A method of making a thin-walled metal can comprising the steps of:

(a) forming a metal disk;

(b) drawing the metal disk to form a shallow cup;

(c) applying the metalworking formulation of claim 1 to the shallow cup;

(d) redrawing and wall ironing the shallow cup to form a thin-walled tubular can body having an open end and an opposing closed end; and

(e) washing the metalworking formulation off the thin-walled tubular can body.

50

36. The method of claim 35, wherein steps (c) and (d) are performed without applying a hydrocarbon-based lubricant.

37. The method of claim 35, wherein steps (c) and (d) are performed by applying a mineral oil at no more than 1 wt. % of the metalworking composition.

38. The method of claim 35, wherein step (c) is performed in a bodymaker, and the metalworking formulation rejects gear oil components from the bodymaker.

39. The method of claim 35, wherein step (b) is performed in a cupper, and the metalworking formulation rejects gear oil components from the cupper or the coil.

51