Boron-free water-based lubricant for plastic processing

Abstract

The present disclosure is directed to an aqueous lubricating composition having utility in cold working of metal substrates, the aqueous lubricating composition comprising the following, based on the weight of the composition: 1 to 20 wt. % of a) at least one water soluble inorganic salt, the inorganic salt being in a dissolved state; b) at least one particulate solid lubricant; 0.1 to 5 wt. % of c) at least one rheology control agent; 0.1 to 5 wt. % of d) at least one base; and 0.1 to 5 wt. % of e) at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and zwitterionic surfactants, wherein the composition is free of boron and boron compounds, and the weight ratio of b) the at least one solid lubricant to a) the at least one water soluble inorganic salt [(b):(a)] is from 0.1:1 to 1:1.

Description

[Technical field]

[0001] The present disclosure is directed to an aqueous lubricating composition for use in cold working of a metal substrate. More particularly, the present disclosure is directed to an aqueous lubricating composition having dispersed therein a particulate solid lubricant to be deposited on a surface of the metal substrate, the aqueous lubricating composition being free of boron compounds. [Background technology]

[0002] The practice of cold working refers to the plastic deformation of metals performed below their recrystallization temperature. In most manufacturing environments, this cold working is performed at room temperature, but the use of temperatures slightly above room temperature (but still below the recrystallization temperature) can increase the ductility and decrease the strength of the metal being worked.

[0003] Broadly, the major cold working operations can be classified under four headings: squeezing, bending, shearing, and drawing. Drawing includes tube, bar, wire, and shell drawing, as well as spinning and ironing. Focusing on the squeezing processes, as they account for the largest tonnage of the processed product, these are generally the processes that involve hot working and include cold rolling, swaging, cold forging, and extrusion.

[0004] These cold working processes have many advantages over hot working processes, the most obvious being the elimination of the energy expenditure of heating, but other advantages include superior surface finish of the worked metal, superior dimensional control of the worked metal, minimization of directional properties of the worked metal, increased strength of the worked metal, and superior reproducibility of the cold working process.

[0005] However, there are disadvantages associated with cold working methods, including the need to generate large forces to deform the metal (especially when the metal has limited ductility), promoting the need for heavier and more powerful processing equipment; the metal surface must be clean and scale-free; strain hardening can occur; and undesirable residual stresses can be present in the processed metal.

[0006] Considering these shortcomings, it is somewhat common in the art to provide metals being cold worked with a lubricating film at the interface between said metal and the cold working tool. An effectively applied lubricating film, which is free of defects and has a consistent and sufficient thickness, can serve to reduce friction at this interface and inhibit the occurrence of seizure. Experience in the art has demonstrated that lubricants are difficult to apply and handle to provide an effective film on metal substrates. As a result, solid lubricating films have come into widespread use. These films can be deposited from solvent-borne or water-based compositions in which the solid lubricant is dispersed.

[0007] GB 2003923A (Foseco Int.) discloses a metal working lubricant composition comprising (i) a water-soluble metal soap, and (ii) an alkali metal chloride, an alkali metal sulfate, and an alkali metal borate.

[0008] WO 00 / 63324 A1 (Chevron Chemical Company) discloses a lubricating oil composition having a base oil of lubricating viscosity, a dispersed hydrated alkali metal borate, and a polyalkylene succinic anhydride or a non-nitrogen derivative thereof.

[0009] EP 917559 A (Henkel) discloses an aqueous lubricant for cold plastic working of metals, which comprises, in addition to water, the following: (a) a water-soluble inorganic salt component; (b) a component in which a solid lubricant is uniformly dispersed; (c) a component in which at least one substance selected from the group consisting of mineral oil, animal and vegetable oils and synthetic oils is uniformly emulsified; and (d) a surfactant, in which the weight ratio of the solid lubricant to the water-soluble inorganic salt ((b) / (a)) is 0.05:1 to 2:1, and the weight ratio of the oil component to the sum of the water-soluble inorganic salt and the solid lubricant ((c):(a+b)) is 0.05:1 to 1:1.

[0010] EP 2450423 A (Henkel AG & Co. KGaA) discloses an aqueous lubricant for plastic working, comprising a resin component (a) containing a copolymer or homopolymer of a monomer having an ethylenically unsaturated bond, including at least maleic anhydride, an inorganic component (b), and a solid lubricant component (c), in which the maleic anhydride moieties of the resin component (a) are blocked with a nitrogen-containing compound at a blocking rate of 10 to 80%, and the unblocked maleic anhydride moieties are neutralized with an alkali component at a neutralization degree of 40 to 100%.

[0011] JP201246684A (Nihon Parkerizing Co., Ltd.) discloses an aqueous lubricant for plastic working of metallic materials, said lubricant comprising: an alkali metal borate (a), wherein the alkali metal borate (a) comprises lithium borate, the molar ratio of lithium to the total alkali metals in the alkali metal borate (a) is 0.1-1.0, and the molar ratio (B / M) of boron (b) to the alkali metal M in the alkali metal borate (a) is 1.5-4.0.

[0012] CN107805541A (Maanshan Tuori Metal Surface Tech Co. Ltd) provides a lubricant for plastic processing, the lubricant comprising, by weight, 10-50% stearic acid; 1-10% borate; 1-10% rust inhibitor; 1-10% inorganic alkali; 0.1-0.5% antifoaming agent; and the balance. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] GB 2003923 [Patent Document 2] International Application Publication No. 00 / 63324 [Patent Document 3] European Patent Application Publication No. 917559 [Patent Document 4] European Patent Application Publication No. 2450423 [Patent Document 5] JP 201246684 A [Patent Document 6] China Patent Application Publication No. 107805541 Summary of the Invention [Problem to be solved by the invention]

[0014] It should be noted that many of these prior arts have in common that they use boron compounds. This is considered to be disadvantageous. Boron compounds are irritating to humans and animals, especially to the nose, throat, and eyes of humans. Large amounts of boron exposure in humans can cause stomach, kidney, and brain infections. Furthermore, boron compounds released into soil from industrial wastewater can supplement the natural boron levels in soil to toxic levels that are very easily reached by leaf-migrating plants. It is difficult to ameliorate such boron toxicity in soil.

[0015] There is a perceived need in the art to develop water-based lubricating compositions that are free of boron and boron compounds, yet retain effective utility in the cold working of metal substrates. [Means for solving the problem]

[0016] According to a first aspect of the present invention, a composition comprising, based on weight of the composition, the following: a) at least one water-soluble inorganic salt, 1-20% by weight, said inorganic salt being in a dissolved state; b) at least one particulate solid lubricant; c) at least one rheology control agent, 0.1-5 wt.%; d) 0.1 to 5% by weight of at least one base; and e) 0.1 to 5% by weight of at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants. Including, Here, there is provided an aqueous lubricating composition, wherein the composition is free of boron and boron compounds, and further characterized in that b) the weight ratio of the at least one solid lubricant to a) the at least one water-soluble inorganic salt [(b):(a)] is from 0.1:1 to 1:1.

[0017] In an important embodiment of the present invention, the aqueous lubricating composition comprises, by weight of the composition, the following: a) said at least one water-soluble inorganic salt, 2-20% by weight, preferably 5-20% by weight, said inorganic salt being in a dissolved state; b) said at least one particulate solid lubricant; c) said at least one rheology control agent, 0.1-2.5 wt.%, preferably 0.1-2 wt.%; d) 0.1 to 2.5% by weight, preferably 0.1 to 2% by weight, of said at least one base; and e) 0.1 to 2.5% by weight, preferably 0.1 to 2% by weight, of at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and zwitterionic surfactants. Including, wherein the composition is further characterized in that it does not contain boron or a boron compound, and the weight ratio of b) the at least one solid lubricant to a) the at least one water-soluble inorganic salt [(b):(a)] is 0.1:1 to 1:1, preferably 0.2:1 to 1:1.

[0018] The aqueous lubricant composition may optionally have a pH of from 7 to 10, preferably from 7 to 9.

[0019] Aqueous lubricating compositions typically contain 60 to 90 wt. %, preferably 65 to 85 wt. %, more preferably 65 to 80 wt. % water, based on the weight of the composition. Instead of, or in addition to, the water content characteristic, the aqueous lubricating composition may be characterized by a viscosity of 0.005 to 1 Pa s, measured using a Brookfield viscometer at 25° C.

[0020] The total amount of rheology control agent c) contained in the composition desirably ranges from 1 to 10% by weight, preferably from 2 to 8% by weight, of the total weight of components a) and b).The or each rheology control agent contained in the composition is preferably a thixotropic agent.

[0021] Exemplary aqueous lubricant compositions according to the present invention may comprise, by weight of the composition, the following: as component a) 5-20% by weight of a mixture of sodium sulfate, potassium tripolyphosphate, and sodium tripolyphosphate, each of the mixture or said salts being in dissolved state; A solid lubricant comprising or consisting of: at least one phosphate selected from the group consisting of zinc phosphate, calcium zinc phosphate, and manganese phosphate; and at least one wax selected from the group consisting of polyethylene wax; oxidized polyethylene wax; polypropylene wax; oxidized polypropylene wax; and copolymer waxes based on ethylene or propylene as the main monomer, Furthermore, said at least one wax is characterized by a number average molecular weight (Mn) of 400 to 30,000 g / mol, preferably 1000 to 25,000 g / mol; c) as components, 0.1 to 2% by weight of at least one thixotropic agent selected from the group consisting of cellulose derivatives; and polysaccharides; d) as a component, 0.1 to 2% by weight of at least one base selected from the group consisting of: Bis(2-(N,N'-dimethylamino)ethyl)ether; Bis-(t-butylaminoethyl)ether; 1,2-bis-(t-butylaminoethoxy)ethane; 1,2-bis-(t-butylaminoethoxy)ethane; Bis[2-(isopropylamino)propyl]ether; 1,2-[2-isopropylamino)-propoxy]ethane; and As component e), 0.1 to 2 wt. % of at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants, The composition is further characterized in that it is free of boron and boron compounds, and b) the weight ratio of the at least one solid lubricant to a) the mixture of water-soluble inorganic salts [(b):(a)] is from 0.2:1 to 1:1, preferably from 0.4:1 to 1:1.

[0022] According to a second aspect of the present invention there is provided the use of an aqueous aqueous lubricating composition as defined hereinabove and in the accompanying claims, or a dry film obtained therefrom, in the plastic cold working of a metallic substrate.

[0023] The present invention further provides a method for plastically cold working a solid metal substrate by mechanically forcing the solid metal substrate through an aperture bounded by at least one solid surface of at least one metalworking tool, the method comprising the steps of: i) applying an aqueous lubricant composition as defined herein and in the appended claims to at least one solid surface of said metal substrate which, if uncoated, will be in direct contact with a solid metalworking tool surface during the process; ii) drying the applied aqueous lubricant composition to form a film on the at least one solid surface of the metal substrate; and iii) mechanically forcing the metal substrate formed in step ii) through said opening bounded by at least one metalworking tool surface such that the metal substrate is cold worked. Includes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] <Definition> As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0025] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," "containing," or "contains" and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps. When used, the term "consisting of" is closed and excludes all additional elements. Moreover, the term "consisting essentially of" excludes additional material elements, permitting the inclusion of non-material elements that do not materially alter the nature of the invention.

[0026] When amounts, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, or preferred upper values ​​and limits, it is to be understood that any range obtained by combining any upper value or preferred value with any lower value or preferred value is also specifically disclosed, regardless of whether the resulting range is expressly stated in the context.

[0027] The terms "preferable," "preferred," "preferably," "particularly," and "desirably" are used frequently herein to refer to embodiments of the present disclosure that may afford certain advantages, under particular circumstances. However, the recitation of one or more preferred, preferred, desirable, or particular embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the present disclosure.

[0028] In this application, the word "may" is used in its permissive (i.e., possible) rather than mandatory sense.

[0029] Room temperature as used herein is 23°C ± 2°C.

[0030] In this specification, number average molecular weight (Mn) and weight average molecular weight (Mw) are determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as eluent according to DIN 55672-1:2007-08. The term polydispersity (PD) is derived from Mw and Mn and is calculated as (Mw / Mn).

[0031] In this specification, the term "average particle size (d 50 ""means a particle size distribution such that at least 50% by weight of the particles have a particle diameter less than the specified value. Unless otherwise specified, particle size is determined by laser diffraction.

[0032] The term "aqueous lubricating composition" as used herein refers to a composition that actually contacts the metal substrate. As known in the art, such contact can occur in a so-called "bath" that is shaped, sized, and arranged to allow at least a portion of the substrate to be immersed therein. The bath is also desirably sized to allow movement of the aqueous lubricating composition around and throughout the loaded substrate, which movement can be further enhanced using recirculation and / or ultrasound. The pH of the composition in the bath, the temperature of the bath, and the substrate contact time are result effective variables that are desirably monitored, whenever possible, either manually or automatically.

[0033] As used herein, the term "alloy" refers to a material composed of two or more metals, or metals and nonmetals, intimately bound together, usually by fusing or dissolving together when melted. Thus, the term "X alloy" refers to an alloy in which metal X is the majority constituent, with X generally comprising at least 40% by weight, more typically at least 50% or at least 60% by weight of the alloy on a metal basis.

[0034] As used herein, "C1-C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, i.e., an alkane group, and includes straight-chain and branched organic groups. Thus, "C1-C 18 An "alkyl" group refers to a monovalent group containing 1 to 18 carbon atoms, i.e., an alkane group, including straight chain and branched organic groups. Examples of alkyl groups include, but are not limited to, methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given moiety (R), the tolerance of one or more non-halogen substituents in an alkyl group is described in the specification.

[0035] As used herein, "C1-C n The term "hydroxyalkyl" refers to a HO-(alkyl) group having 1 to n carbon atoms, where the point of attachment of the substituent is through the oxygen atom and the alkyl group is as defined above.

[0036] "Alkoxy group" refers to a monovalent group represented by -OA, where A is an alkyl group; non-limiting examples of which are methoxy, ethoxy, and iso-propyloxy. As used herein, "C-C 12 The term "alkoxyalkyl" refers to an alkyl group having an alkoxy substituent, as defined above, where the moiety (alkyl-O-alkyl) contains a total of 1 to 12 carbon atoms; such groups include methoxymethyl (-CHOCH), 2-methoxyethyl (-CHCHOCH), and 2-ethoxyethyl.

[0037] The term "alkylene" as used herein is defined as a saturated divalent hydrocarbon radical. In general in this disclosure, such alkylene groups may be unsubstituted or substituted with one or more halogens.

[0038] "C3-C 30 The term "cycloalkyl" is understood to mean a saturated monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms. In the present invention, such cycloalkyl groups may be unsubstituted or substituted with one or more halogens. Where applicable for a given moiety (R), the tolerance of one or more non-halogen substituents in a cycloalkyl group is described herein. Examples of cycloalkyl groups include cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0039] As used herein, "cycloalkylene" means a divalent radical formed by removing two hydrogen atoms from one or more rings of a cycloalkyl group.

[0040] As used herein, the term "C-C alkyl group" used alone or as part of a larger moiety (such as an "aralkyl group") means a C-C alkyl group. 18 An "aryl" group refers to a monocyclic, bicyclic or tricyclic ring system in which the monocyclic ring system is aromatic or at least one of the rings of the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzo-fused 2-3 membered carbocyclic rings. In the present invention, such aryl groups may be unsubstituted or substituted with one or more halogens. The tolerance of one or more non-halogen substituents in an aryl group, where applicable for a given moiety (R), is described herein. Exemplary aryl groups include: phenyl; (C1-C4) alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. It may also be mentioned that the phenyl group is preferred.

[0041] "Arylene," when used independently or in conjunction with a linking moiety such as alkarylene, means a divalent group formed by the removal of two hydrogen atoms from one or more rings of an aryl group as defined above, where the hydrogen atoms may be removed from the same or different rings. Representative examples include phenylene and naphthylene.

[0042] As used herein, "C 2- C 20 "Alkenyl" means a hydrocarbyl group having 2 to 20 carbon atoms and at least one unit of ethylenic unsaturation. Alkenyl groups may be straight chained, branched, or cyclic and may be optionally substituted with one or more halogens. Where applicable to a given moiety (R), tolerance for one or more non-halogen substituents within an alkenyl group is described herein. The term "alkenyl" also encompasses groups having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as will be appreciated by those of skill in the art. The above C 2- C 20Examples of alkenyl groups include, but are not limited to, -CH=CH2; -CH=CHCH3; -CH2CH=CH2; -C(=CH2)(CH3); -CH=CHCH2CH3; -CH2CH=CHCH3; -CH2CH2CH=CH2; -CH=C(CH3)2; -CH2C(=CH2)(CH3); -C(=CH2)CH2CH3; -C(CH3)=CHCH3; -C(CH3)CH=CH2; -CH=CHCH2CH2CH3; -CH2CH=CHCH2CH3 ;-CH2CH2CH=CHCH3;-CH2CH2CH2CH=CH2;-C(=CH2)CH2CH2CH3;-C(CH3)=CHCH2CH3;-CH(CH3)CH=CHCH;-CH(CH3)CH=CHCH;-CH(CH3)CH2CH=CH2;-CH2CH=C(CH3)2;1-cyclopent-1-enyl;1-cyclopent-2-enyl;1-cyclopent-3-enyl;1-cyclohex-1-enyl;1-cyclohex-2-enyl; and, 1-cyclohex-3-enyl.

[0043] The term "alkenylene" means a divalent group formed by removal of two hydrogen atoms from an alkenyl group that is defined above.

[0044] As used herein, "alkylaryl" refers to an alkyl-substituted aryl group, both of which are as defined above. Additionally, as used herein, "aralkyl" refers to an alkyl group substituted with an aryl radical, as defined above.

[0045] The term "hetero" as used herein refers to groups or moieties that include one or more heteroatoms, such as N, O, Si, and S. Thus, for example, a "heterocycle" refers to a cyclic group having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl," "heterocycloalkyl," and "heteroaryl" moieties are alkyl, cycloalkyl, and aryl groups, as defined herein, that include N, O, Si, or S, respectively, as part of their structure.

[0046] The term "base" as used herein refers to a species that can abstract a proton or donate a hydroxide anion (OH-) in either a polar or non-polar solvent.

[0047] The term "amine" is used according to its normal meaning in the art and generally refers to a compound that contains a nitrogen atom having an unshared lone pair of electrons.

[0048] As used herein, "C1-C9 heteroarylamine" refers to a compound in which at least one carbon atom of an aromatic ring (which may be a monocyclic or polycyclic ring system) is replaced with a nitrogen atom. Preferably, C1-C9 heteroarylamines have 1-3 carbon atoms of the aromatic ring substituted with a nitrogen atom. Heteroarylamines may be unsubstituted or substituted with one or more C1-C4 alkyl groups at any position of the heteroaryl ring. In addition to having at least one carbon atom of the hydrocarbon ring substituted with a nitrogen atom, heteroarylamines may also have one or more carbon atoms substituted with other heteroatoms. Examples of heteroarylamines include, but are not limited to, pyridine, pyrrole, pyrimidine, imidazole, quinazoline, purine, pyrazole, and triazole.

[0049] As used herein, the term "C1-C9 heterocyclic amine" refers to an aliphatic compound, which may be monocyclic or polycyclic, in which at least one carbon atom (preferably one or two carbon atoms) of a given hydrocarbon ring is replaced with a nitrogen atom. The total number of ring carbon atoms is 1 to 9. Heterocyclic amines can be unsubstituted or substituted with one or more C1-C4 alkyl groups as defined above at any position of the heterocycle, including one or more nitrogen atoms. In addition to having at least one carbon atom of the hydrocarbon ring replaced with a nitrogen atom, heterocyclic amines may have one or more carbon atoms replaced with other heteroatoms. Examples of heterocyclic amines include, but are not limited to, piperazine, pyrrolidine, and morpholine.

[0050] An "amino acid" is an organic acid having one or more alkaline groups, such as amino, guanidino, imino, or hydrazine groups, attached to any carbon atom other than the carboxyl group. As used herein, the term "basic amino acid" refers to an amino acid that further has an alkaline group capable of accepting a proton. Examples of basic amino acids include, but are not limited to, arginine and lysine, including both the L- and D-forms of each.

[0051] As used herein, the term "amino sugar" refers to a monosaccharide unit having one or more hydroxyl groups replaced with an -NR2 group, where each R is independently selected from H or C1-C4 alkyl. Examples of amino sugars include, but are not limited to, glucosamine and N-methylglucamine.

[0052] The viscosity of the composition may be measured using a Brookfield Viscometer, Model RVT, under standard conditions of 20° C. and 50% relative humidity (RH). The viscometer is calibrated using silicone oils of known viscosity varying from 5,000 cps to 50,000 cps. Calibration uses a set of RV spindles that are attached to the viscometer. Measurements of the aqueous lubricating compositions are taken using a No. 6 spindle at a speed of 20 revolutions per minute for one minute until the viscometer is equilibrated. The viscosity corresponding to the equilibrated measurement is then calculated using the calibration.

[0053] The compositions of the present invention are defined herein as being "substantially free" of a particular compound, element, ion, or other similar component. The term "substantially free" is intended to mean that the compound, element, ion, or other similar component is not intentionally added to the composition and is present in only trace amounts at most that do not affect (adversely affect) the desired properties of the coating. An exemplary trace amount is less than 1000 ppm by weight of the composition. The term "substantially free" encompasses the term "free," with the latter term encompassing embodiments in which the particular compound, element, ion, or other similar component is completely absent from the composition or is absent in any amount measurable by techniques commonly used in the art.

[0054] <Detailed Description of the Invention> [a) Water-soluble inorganic salt] The aqueous lubricating composition of the present disclosure comprises, based on the weight of the composition, 1 to 20 wt. % of a) at least one water-soluble inorganic salt. The aqueous lubricating composition preferably comprises 2 to 20 wt. %, for example 5 to 20 wt. %, of said at least one water-soluble inorganic salt. The or each water-soluble inorganic salt is in a dissolved state in the aqueous lubricating composition.

[0055] The chemical nature of the salt is not critical, other than the fact that inorganic salts containing boron (e.g., borates, etc.) are excluded. It is desirable for the water-soluble inorganic salt to form a coating on the metal substrate being cold worked.

[0056] Non-limiting examples of suitable water-soluble inorganic salts that may be used alone or in combination in the present disclosure include: phosphates, such as calcium phosphate; polyphosphates, including alkali metal polyphosphates; alkali metal silicates, particularly sodium silicate and potassium silicate; alkali metal tungstates, particularly sodium tungstate; molybdates, including ammonium molybdate and alkali metal molybdates, particularly sodium molybdate; sulfates, including alkali metal sulfates, particularly sodium sulfate and potassium sulfate; and carbonates, including alkali metal carbonates, particularly sodium carbonate or potassium carbonate.

[0057] For completeness, the term "polyphosphate" refers to a group containing at least two, e.g., 2 to 6, tetrahedral phosphoric acid (PO4) units linked together through a shared oxygen atom; the polyphosphate may be linear or cyclic. Exemplary alkali metal polyphosphates having utility in the present disclosure include, but are not limited to, tetrasodium pyrophosphate; tetrapotassium pyrophosphate; sodium tripolyphosphate; potassium tripolyphosphate; sodium metaphosphate; potassium metaphosphate; sodium hexametaphosphate; potassium hexametaphosphate; lithium hexametaphosphate; and mixtures thereof.

[0058] In the present disclosure, good results are obtained when component a) comprises a mixture of sodium sulfate, potassium tripolyphosphate and sodium tripolyphosphate.

[0059] [b) Solid lubricant] The aqueous lubricating composition comprises b) at least one particulate solid lubricant. The lubricant particles are usually dispersed in the composition: the composition is applied to the surface of the substrate to be processed and then dried thereon, the particles being deposited on the surface. Depending on the nature of the solid lubricant, coalescence of the deposited particles may occur on drying, leading to the development of a lubricating film on the substrate surface.

[0060] The weight ratio [(b):(a)] of b) said at least one particulate solid lubricant to a) said at least one water-soluble inorganic salt in the aqueous lubricant is preferably in the range of 0.1:1 to 1:1. Preferably, said weight ratio [(b):(a)] is in the range of 0.2:1 to 1:1, in particular 0.4:1 to 1:1 or 0.4:1 to 0.8:1. The specific value of this ratio is preferably selected based on the specific shape of the metal stock to be subjected to plastic processing, the processing conditions and the processing equipment. If the weight ratio is less than 0.1:1, the lubricity of the resulting coating is reduced, and scuffing and seizure of the metal workpiece occurs. If the weight ratio exceeds 1:1, the hardness of the coating is reduced and the adhesion between the substrate and the coating is reduced: if the metal is introduced into the opening of the tool under such circumstances, the dried coating formed on the surface is very prone to peeling, and as a result, the lubricity is impaired.

[0061] Without intending to limit this disclosure, particulate solid lubricants are conventionally selected from: i) lamellar solids including talc, mica, graphite, zinc sulfide (ZnS), cadmium sulfide (CdS), molybdenum disulfide (MoS2), molybdenum selenide (MoSe2); tungsten disulfide (WS2), selenium disulfide (SeS2), calcium fluoride (CaF2), and sodium-aluminum fluoride, e.g., cryolite and modified cryolite as disclosed in U.S. Pat. No. 3,377,279; iii) metal soaps including metal salts of fatty acids, e.g., lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, and behenic acid; iii) lubricating oxides including titanium oxide, cadmium oxide, cobalt oxide, zinc oxide, and silica (SiO2); iv) non-lamellar, lubricious metallic compounds. Particulate lubricants include, for example, cerium fluoride (CeF3), calcium hydroxide, calcium carbonate, zinc phosphate, calcium zinc phosphate, and manganese phosphate; v) soft elemental metals, including gold, silver, lead, tin, indium, and barium; vi) solid polymeric lubricants, including polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), polyacetal, polyimide, polyether ether ketone (PEEK), and ultra-high molecular weight polyethylene (UHWPE); and vii) waxes. Such particulate lubricants may be used alone or in combination.

[0062] For the sake of completeness, the term "mica" above includes both synthetic micas and natural micas such as sericite and muscovite. Furthermore, metal soaps conventionally contain calcium, aluminum, magnesium, barium, zinc, lead, lithium or potassium as constituent metals; it may be mentioned that the use of calcium stearate as metal soap is preferred.

[0063] Without intending to limit the invention, exemplary waxes having utility in aqueous lubricating compositions include: paraffin wax [CAS No. 8002-74-2]; polyethylene wax [CAS No. 9002-88-4]; polyethylene-polypropylene wax; copolymerized polyethylene waxes, such as copolymers of ethylene and at least one monomer selected from (meth)acrylic acid, maleic anhydride, vinyl acetate, and vinyl alcohol, which are available, for example, under CAS Nos. 38531-18-9, 104912-80-3, and 219843-86-4; polybutene wax; Fischer-Tropsch wax; oxidized waxes, such as oxidized polyethylene wax [CAS No. 68441-17-8]; polar modified polypropylene waxes; microcrystalline waxes, such as microcrystalline paraffin wax [CAS No. 63231-60-7]; montan wax and montan wax raffinate; montanic acid and its salts and esters; fatty acid amides, such as erucamide [CAS No. 112-84-5], oleamide [CAS No. 301-02-0] and 1,2-ethylenebis(stearamide) [CAS No. 110-30-5]; and carnauba wax.

[0064] The wax contained in the composition preferably meets at least one of the following conditions: i) an acid number of less than 200 mg KOH / g, preferably less than 100 mg KOH / g; ii) a melting point of 40-200° C., preferably 60-180° C.; and iii) a number average molecular weight (Mn) of at least 200 g / mol, preferably at least 400 g / mol. For completeness, these conditions are not intended to be mutually exclusive: a wax may meet one, two or desirably three of these conditions.

[0065] Particular preference may be given to the use of at least one wax selected from polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, and copolymer waxes based on ethylene or propylene as the main monomer. For example, in exemplary embodiments, the solid lubricant comprises or consists of: at least one phosphate selected from the group consisting of zinc phosphate, calcium zinc phosphate, and manganese phosphate; and at least one wax selected from polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, and copolymer waxes based on ethylene or propylene as the main monomer. In these embodiments, the or each wax contained in the composition is desirably further characterized by a number average molecular weight (Mn) of 400 to 30,000 g / mol, preferably 1000 to 25,000 g / mol.

[0066] To facilitate their inclusion in the aqueous compositions of the present invention, the or each solid particulate lubricant is initially provided in the form of: i) a finely divided powder, in particular having a dot size of less than 5 microns as measured by laser diffraction; 50 and / or ii) as an aqueous dispersion, the particles of which desirably have a d of less than 5 microns as measured by dynamic light scattering. 50 In an exemplary embodiment, the or each solid particulate lubricant included in the aqueous composition has a particle size of less than 2 microns, preferably less than 1 micron, as measured by laser diffraction. 50 The particle may be included.

[0067] [c) Rheology control agent] The aqueous lubricating composition of the present disclosure comprises 0.1 to 5 wt. % of c) at least one rheology control agent, based on the weight of the composition. The aqueous composition may preferably comprise 0.1 to 2.5 wt. %, for example 0.1 to 2 wt. % of c) said at least one rheology control agent.

[0068] In certain embodiments, the total amount of rheology control agent c) present in the composition desirably ranges from 1 to 10% by weight, such as from 2 to 8% by weight, of the total weight of components a) and b).

[0069] The term "rheology control agent" as used herein refers to a compound that can absorb liquids, such as, but not limited to, water, and physically swell, thereby changing the viscosity and flow properties of the liquid. Rheology control agents can also function as thickeners, typically by forming a continuous phase matrix, and can serve to maintain the components of the composition, particularly solid lubricants, in a dispersed form. The agent can also function to modify the drying properties of the composition.

[0070] In particular, it is noted that the or each rheology control agent included in the composition is desirably a thixotropic agent, which, according to its standard definition, is a material that, when dispersed in a solvent, here water, exhibits a viscosity that, on its own, decreases when subjected to stress, such as when stirred.

[0071] Without intending to limit the invention, it is preferred that the at least one rheological agent is selected from the group consisting of clays such as smectite clays, synthetic hectorite clays, colloidal montmorillonite, silicoaluminate clays and colloidal magnesium aluminum silicates derived from natural smectite clays; fumed silica (pyrogenic silica); carboxyl vinyl polymers; polyvinylpyrrolidone (PVP) polymers and copolymers such as PVP / vinyl acetate copolymers; polyacrylates; cellulose derivatives such as carboxymethylcellulose (CMC), carboxyhydroxymethylcellulose, ethoxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose; natural thickeners such as alginic acid, guar gum, starch, tragacanth gum, and locust bean gum; polysaccharides such as xanthan gum; and proteins such as casein, collagen, and albumin.

[0072] When particulate rheology control agents are included in the composition, they should have a d of less than 5 microns, especially less than 2 microns, as measured by laser diffraction. 50 It is preferred that the clays are initially provided in a finely divided form characterized by a particle size, for example, fumed silica, natural clays, and synthetic clays, when provided for inclusion in the composition, have a particle size of 5 to 100 nm, e.g., 5 to 40 nm, as measured by laser diffraction. 50 It is desirable to characterize the particle size.

[0073] Regardless of the above, the use of cellulose derivatives and / or polysaccharides as rheology control agents appears to be preferred. For example, good results have been obtained with respect to the stability and shelf life of aqueous lubricating compositions when the aqueous composition comprises at least one, preferably both, of carboxymethylcellulose (CMC) and xanthan gum.

[0074] [d) Base] To provide biostability and rust resistance, the aqueous lubricating composition of the present disclosure comprises 0.1 to 5 wt. % d) of at least one base, based on the weight of the composition. The aqueous lubricating composition may preferably comprise 0.1 to 2.5 wt. %, for example 0.1 to 2 wt. % d) of said at least one base.

[0075] In certain embodiments, which are not intended to be mutually exclusive with the above preferred weight ranges, it is desirable for the amount of base added to be such that the aqueous lubricant composition has a pH of 7 to 10, such as 7 to 9.

[0076] Typically, the or each base present in the composition is one of the following: Alkali metal alkoxides; ammonia; General formula (NR a 4) + (OH) - A quaternary ammonium hydroxide compound having the formula: a are independently selected from C1-C4 alkyl; General formula N(R b )(R c )(Rd aliphatic, aromatic, or mixed aliphatic-aromatic monoamines having the formula b is C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C2-C 12 Alkoxyalkyl, C3-C 18 Cycloalkyl, C2-C 12 Alkenyl, C6-C 10 Aryl, C7-C 18 Aralkyl or C7-C 18 R is alkylaryl; c and R d are independently hydrogen, C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C2-C 12 Alkoxyalkyl, C3-C 18 Cycloalkyl, C2-C 12 Alkenyl, C6-C 10 Aryl, C7-C 18 Aralkyl or C7-C 18 alkylaryl]; Aliphatic, aromatic, or mixed aliphatic-aromatic polyamines, where two or more amino groups -N(R c )(R d ), (these amino groups may be the same or different, R c and R d is as defined above) are linked by an alkylene group, a hydroxyalkylene group, an alkoxyalkylene group, a cycloalkylene group, an alkenylene group, an arylene group, an aralkylene group, or an alkylarylene group; C1-C9 heterocyclic amines; C1-C9 heteroarylamines; Basic amino acids, such as arginine and lysine; and Amino sugars; is selected from the group consisting of:

[0077] Suitable alkali metal alkoxides are usually selected from aliphatic, aromatic or araliphatic alkoxides of lithium, sodium or potassium, non-limiting examples of which are lithium, sodium or potassium methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, sec-butoxide, tert-butoxide, n-pentoxide, isopentoxide, hexoxide, amyl alkoxide, 3,7-dimethyl-3-octoxide, phenoxide, 2,4-di-tert-butylphenoxide, 2,6-di-tert-butylphenoxide, 3,5-di-tert-butylphenoxide, and 2,4-di-tert-butyl-4-methylphenoxide. The use of aliphatic (C1-C4) alkoxides, in particular the methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, sec-butoxide and tert-butoxide of sodium, potassium or lithium, is preferred.

[0078] As mentioned above, the composition may optionally include ammonia (NH3) as a base, either independently or in combination with other bases from among the listed bases. For completeness, the constituent weight of ammonia contained in the composition is calculated on the basis of NH3. Ammonia will be present in the aqueous composition of the present invention as an ammonia solution NH3 (aq), which includes a weakly basic solution of ammonia in water, which may be referred to in the art as ammonium hydroxide, aqueous ammonia, ammonia liquor, aqua ammonia, aqueous ammonia, or simply ammonia. The term "ammonium hydroxide" refers to the ammonia solution [NH4 + ][OH - ], but except in extremely dilute aqueous ammonia solutions, these ions do not constitute a significant portion of the total ammonia in the aqueous ammonia solution, making it virtually impossible to isolate a sample of NH4OH.

[0079] Without intending to limit the disclosure, suitable basic amines that may be included alone or in combination in the aqueous lubricating composition include the following: methylamine; dimethylamine; trimethylamine; ethylamine; diethylamine; triethylamine; cyclohexylamine; dimethylcyclohexylamine; ethanolamine; 2-(diethylamino)ethanol; N,N-dimethylethanolamine, 2,2'-dihydroxydiethylamine (diolamine); N-methylpiperidine; pyridine; 2,6-dimethylpyridine; 2,4,6-trimethylpyridine; quinoline; piperazine; pyrrolidone; 1-(2-hydroxyethyl) )pyrrolidine;morpholine;N-methylmorpholine;4-(2-hydroxyethyl)morpholine;bis(2-(N,N'-dimethylamino)ethyl)ether;bis-(t-butylaminoethyl)ether, 1,2-bis-(t-butylaminoethoxy)ethane;1,2-bis-(t-butylaminoethoxyethoxy)ethane;bis[2-(isopropylamino)propyl]ether;1,2-[2-isopropylamino)-propoxy]ethane;aniline;N-methylaniline;4-methylaniline;4-hydroxylaniline;pyrrole;pyrimidine;imidazole;quinazoline;purine;pyrazole;and triazole.

[0080] Good results have been obtained when the composition comprises at least one base selected from the group consisting of: bis(2-(N,N'-dimethylamino)ethyl)ether; bis-(t-butylaminoethyl)ether, 1,2-bis-(t-butylaminoethoxy)ethane; 1,2-bis-(t-butylaminoethoxyethoxy)ethane; bis[2-(isopropylamino)propyl]ether; 1,2-[2-isopropylamino)-propoxy]ethane. It can be seen that the use of bis(2-(N,N'-dimethylamino)ethyl)ether is particularly preferred.

[0081] [e) Surfactant] The aqueous lubricating composition comprises 0.1 to 5 wt. % of e) at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants, based on the weight of the composition. The composition may comprise 0.1 to 2.5 wt. %, for example 0.1 to 2 wt. %, based on the weight of the composition, of e) said at least one surfactant.

[0082] Suitable nonionic surfactants having utility in the present disclosure include: C5-C 25 Condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide per mole of said alcohol, where the alkylene chain of the aliphatic alcohol may be linear or branched, primary or secondary; alkyl polyglycosides; alkyl glycerol ethers; sorbitan esters; and fatty acid amide surfactants. Examples of commercially available non-ionic surfactants include Neodol® 91-5, Neodol® 91-8, and Neodol® 23-5 (Shell International Research Maatschappij BV); Lutensol A7N, Lutensol XP 50, Lutensol XL150, Lutensol® XL70, Lutensol® T07, and Lutensol® ON50 (BASF); Novel 1412-7, Isalchem®, Lial®, and Marlipal® O13 / 70 (Sasol).

[0083] Suitable amphoteric and zwitterionic surfactants include those having the general formula (R m R n R o NO), wherein R m is C1-C 18 is alkyl, R n and R ois independently selected from C1-C4 alkyl, C1-C4 hydroxyalkyl, and C1-C6 alkoxyalkyl; and, betaines, such as alkyl betaines, carbobetaines, alkylamido betaines, amidazolinium betaines, sulfobetaines, and phosphobetaines. Examples of betaines include: Examples of suitable betaines include, but are not limited to, behenamidopropyl betaine; canolamidopropyl betaine; capramidopropyl betaine; cocamidoethyl betaine; cocamidopropyl betaine; cocamidopropyl hydroxysultaine; oleamidopropyl betaine; isostearamidopropyl betaine; lauramidopropyl betaine; lauryl betaine; lauryl hydroxysultaine; lauryl sultaine; myristamidopropyl betaine; myristyl betaine; oleamidopropyl betaine; oleamidopropyl hydroxysultaine; oleyl betaine; oleylamidopropyl betaine; palmidopropyl betaine; palmitamidopropyl betaine; ricinoleamidopropyl betaine; stearamidopropyl betaine; and stearyl betaine.

[0084] Suitable anionic surfactants are sulfates, sulfosuccinates, sulfoacetates and / or sulfonates. Exemplary sulfonate surfactants include: C6-C 18 Alkyl sulfonates (paraffin sulfonates); C6-C 18 Alkylbenzenesulfonate; C6-C 18 Alkyl glyceryl sulfonates; methyl ester sulfonates (MES); and alpha olefin sulfonates (AOS). However, the anionic surfactants C6-C 18 Alkyl sulfates, C6-C 18 It is preferred to use the water-soluble salts of hydroxyalkyl sulfates and alkyl ethoxy sulfates with an ethoxylation degree of 1 to 5, either alone or in combination.

[0085] Suitable cationic surfactants are generally quaternary ammonium surfactants, particularly monoN-C6-C groups in which the remaining N positions are substituted with C1-C3 alkyl groups or C1-C3 hydroxyalkyl groups. 18 Alkyl or N-C6-C 18 The quaternary ammonium surfactant is selected from the group consisting of alkenyl ammonium surfactants. 18 Alkyl ester or C6-C 18 Alkenyl esters may also be mentioned.

[0086] [Secondary ingredient] The aqueous lubricating compositions of the present disclosure may further include adjuvants and additives that can provide these compositions with improved properties. The adjuvants and additives may, for example, provide one or more of the following: enhanced boundary lubricity; reduced drying time; reduced corrosivity; improved stability; and extended shelf life of the composition. Such adjuvants and additives may be used in any combination and proportion desired, as long as they do not adversely affect the properties and essential characteristics of the composition. Although exceptions may exist in some cases, it is desirable that these adjuvants and additives as a whole do not comprise more than 5% by weight of the total weight of the aqueous lubricating composition.

[0087] Such adjuvants and additives include: anti-wear additives; corrosion inhibitors; antioxidants; free fatty acids, which may act to form a reaction layer for boundary lubrication; optical brighteners, especially where visibility of solid lubricant deposits under lighting may be required; and tackifiers.

[0088] The addition of oil helps to form an oily surface on the substrate surface after the aqueous composition dries, and can compensate for the loss of lubricating performance in areas of the workpieces that are characterized by non-uniform film deposition of solid lubricants.Furthermore, in the embodiment of the composition where the aqueous lubricating composition is applied at high temperature, this is typically achieved by heating the lubricant with a steam tube.The addition of oil to the aqueous lubricating composition can inhibit the adhesion of solid particle lubricants to the heating tube.

[0089] The oils may be used alone or in combination and may be selected from mineral oils, animal oils, animal fats, vegetable oils and synthetic oils, however, it is preferred that the or each added oil is typically characterized by at least one, and preferably all, of the following: a flash point in the range of 150 to 300°C; a melting point of -20 to 20°C; and a viscosity of 5 to 100 centistokes strokes measured at 40°C.

[0090] A melting point of more than 20°C may result in a decrease in the emulsifying and re-emulsifying ability of the oil in the aqueous lubricant, and thus may tend to decrease the stability of the treatment bath. An oil component having a melting point of less than -20°C usually has a decreased flash point. Similarly, a viscosity of less than 5 centistokes usually has a low flash point, which results in the generation of a large amount of gas after operation, creating a risk of fire. Similarly, when the viscosity of the additive oil is less than 5 centistokes, the slip between solid lubricant particles decreases, and lubricating performance tends to decrease. Conversely, a viscosity of more than 100 centistokes usually results in a decrease in the emulsifying and re-emulsifying ability of the oil component in the aqueous lubricant.

[0091] Tackifiers are utilized to improve the rate of lubricant migration and ensure that the applied and dried lubricating composition stays in place and provides the required lubrication. The or each tackifier resin included in the composition is preferably characterized by: a softening point of 70 to 150°C; and a viscosity at 150°C of less than 2000 Pa·s.

[0092] Exemplary tackifying resins that may be used alone or in combination in the present invention include: aliphatic and cycloaliphatic petroleum hydrocarbon resins; aromatic petroleum hydrocarbon resins and their hydrogenated derivatives; aliphatic / aromatic petroleum derived hydrocarbon resins and their hydrogenated derivatives; polycyclopentadiene resins, hydrogenated polycyclopentadiene resins, and aromatic modified hydrogenated polycyclopentadiene resins; terpenes, aromatic terpenes and hydrogenated terpenes; polyterpenes, aromatic modified polyterpenes, and terpene phenols; copolymers of α-methylstyrene and additional vinyl aromatic monomers; and gum rosin, gum rosin esters, wood rosin, wood rosin esters, tall oil rosin, tall oil rosin esters and hydrogenated rosin esters.

[0093] <Preparation of Aqueous Composition> The aqueous lubricating composition is formulated by simply mixing the various components and auxiliary components. Although the order of mixing the components is not limited, it would be prudent to first form an aqueous dispersion of the rheology control agent (c) and then add the inorganic salt (a), the solid lubricant (b) and any further components to the dispersion under stirring. Desirably, the solid lubricant (b) is added after both the rheology control agent (c) and the inorganic salt to ensure that a stable and uniform dispersion is formed. As mentioned above, it may be advantageous to pre-prepare the particulate and polymeric components as aqueous dispersions, for example at a solids content of 45-60% by weight, to facilitate blending with the other components of the composition. The inorganic salt a) may be added as a pre-prepared solution or in solid form, but under mixing conditions that ensure that the salt is in dissolved form in the final aqueous lubricating composition.

[0094] If necessary, the aqueous lubricating composition can be prepared fully prior to its application. However, in an interesting alternative embodiment, a concentrated composition may first be obtained by mixing the components with only a portion of the water that will be present in the composition to be applied: the concentrated composition may then be diluted with the remaining water immediately prior to application. It is envisaged that such concentrated compositions can be prepared and stored as single-packed concentrates (which can be converted by dilution with water only) or as multi-packed concentrates, two or more of which must be combined and diluted to form the complete working composition according to the invention. Dilution can be carried out by simply adding water, in particular deionized water and / or demineralized water, under mixing.

[0095] While there is no particular intent to limit the amount of water contained in the aqueous lubricating composition, it is preferred that the composition contains 60 to 90 wt. %, preferably 65 to 85 wt. %, more preferably 65 to 80 wt. % water based on the weight of the composition. In an alternative, but not mutually exclusive, feature, the aqueous lubricating composition may be defined by a viscosity of 0.005 to 1 Pa s (50 cps to 1000 cps) measured using a Brookfield viscometer at 25°C.

[0096] <Methods and Applications> Before applying the composition to a metal substrate, it is often desirable to pretreat the relevant surface to remove foreign matter therefrom. If applied, this step may promote the subsequent adhesion of the composition thereto. Such treatments are known in the art and can be carried out in a single or multi-step process consisting, for example, of the use of one or more of the following: etching treatment with an acid suitable for the substrate, and optionally an oxidizing agent; ultrasonic treatment; plasma treatment, including, for example, chemical plasma treatment, corona treatment, atmospheric plasma treatment and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as acetone, carbon tetrachloride or trichloroethylene; and rinsing with water, preferably deionized water or pure water. Of these examples, when an aqueous alkaline degreasing bath is used, it is desirable to remove the degreaser remaining on the surface by rinsing the substrate surface with deionized water or pure water.

[0097] After said cleaning and / or degreasing, an aqueous lubricating composition is applied to the substrate. The composition may be applied at ambient temperature or the temperature of the aqueous composition may be raised prior to application, for example to a temperature in the range of from 30° C. to 90° C., for example from 30° C. to 70° C.

[0098] To produce double-sided plated sheets, it is commercially common to prepare an operating bath as described above and apply the aqueous lubricating composition to the substrate by, but not limited to, immersion and dipping. The contact time of the aqueous lubricating composition is not critical, but should be long enough for the temperature of the substrate to equilibrate with the temperature of the composition in the operating bath. Exemplary contact times are 1 minute to 15 minutes, such as 2 minutes to 10 minutes.

[0099] Alternative techniques that may be used to apply the aqueous lubricating composition to a single surface or surfaces of a substrate include, but are not limited to, the following: painting; brushing; flow coating; roll coating; wiping; air atomization spraying; air assisted spraying; airless spraying; high volume low pressure spraying; and air assisted airless spraying.

[0100] At the end of the coating process, the article is dried, for example using ambient air drying, circulating hot air, forced air drying, or infrared heating. The surface temperature of the substrate is controlled during drying: the peak metal temperature (PMT) should not exceed 150°C, and more specifically should be in the range of 100-125°C, e.g., 100-120°C.

[0101] The above-mentioned treatment results in a protective film on the metal substrate, said film preferably having a thickness of 1 to 50 g / m 2 , preferably 1 to 40 g / m 2 , or 5 to 40 g / m 2The optimum thickness of the dry coating is determined by the type of metal processing performed, the degree of processing, and the surface roughness of the substrate. However, generally, if the dry coating is too thin, contact between the processing tool and the substrate itself may occur, making seizure more likely. If the dry coating is too thick, some of the coating may not be drawn into the interface between the processing tool and the substrate, and this portion will therefore be a waste of the water-based lubricant.

[0102] There is no intention to limit the base substrate that the aqueous lubricating composition may be applied to.Therefore, suitable metal substrates include, but are not limited to: iron; titanium; nickel; zinc; copper; aluminum; tin; cobalt; and alloys thereof.Specific examples of substrates that include or consist of steel include galvanized steel and galvanneal steel that meet the requirements of ASTM standard A653; GALVALUME®, 55%Al / 43.4%Zn / 1.6%Si alloy coated steel plate (manufactured by Bethlehem Steel Corporation); and GALFAN®, 5%Al / 95%Zn alloy coated steel plate (manufactured by Weirton Steel Corporation).

[0103] The initial shape of the substrate to which the aqueous lubricating composition is applied also need not be limited, although the form should suit the tooling used and the target shape or form to be achieved after cold working. Conventional stock shapes in which metal and alloy substrates may be provided include: sheets; plates; rectangular prisms; spheres; rings; solid cylinders; tubes; and wires, although more complex shapes are certainly not precluded.

[0104] As noted above, the present disclosure also provides for the use of the aqueous lubricant composition, or a dry film derived therefrom, in the plastic cold working of a metal substrate.

[0105] The present disclosure further provides a method for plastically cold working a solid metal substrate by mechanically forcing said solid metal substrate through an opening bounded by at least one solid surface of at least one metalworking tool, said method comprising the steps of: i) applying an aqueous lubricant composition as defined herein above to at least one solid surface of said metal substrate which surface, if uncoated, will be in direct contact with a solid metalworking tool surface during the process; ii) drying the applied aqueous lubricant composition to form a film on the at least one solid surface of the metal substrate; and iii) mechanically forcing the metal substrate formed in step ii) through said opening bounded by at least one metalworking tool surface such that the metal substrate is cold worked.

[0106] It is recognized that the plastic cold working of metals is usually an iterative process. Thus, the above process may further include the steps of: iv) removing a residual film from said at least one solid surface of the cold worked metal substrate formed in step iii); v) annealing the metal substrate obtained in step iv); and vi) Repeating steps i) to iii).

[0107] In one embodiment, step iv) comprises treating the residual film with an alkaline degreaser. It is particularly preferred that step iv) does not comprise treating the residual film with an acidic pickling solution.

[0108] If the residual lubricant film obtained after step iii) is not removed prior to annealing, the carbon, sulfur, phosphorus and other components of the lubricant film may penetrate into the metal substrate, thereby compromising the corrosion resistance and mechanical strength of the substrate. Moreover, the residual lubricant film will not present a surface to which the aqueous lubricant composition will adhere in the second (and further) repetitions of step i) above.

[0109] Various features and embodiments of the present disclosure are illustrated in the following examples, which are intended to be representative and not limiting. EXAMPLES

[0110] In Example 1, which represents a composition according to the invention, the following commercially available products are used: The remaining components mentioned below are available from Sigma Aldrich.

[0111] TIFF2024540046000001.tif31168

[0112] Aqueous lubricant compositions were prepared by mixing the components shown in Table 1 below. An aqueous solution of inorganic salt (a) was prepared, to which was added rheology control agent (c), base (d) and surfactant, followed by addition of solid lubricant (b), which was added as a previously prepared aqueous dispersion.

[0113] In view of the above description and examples, it will be apparent to those skilled in the art that equivalent modifications can be made without departing from the scope of the claims.

[0114] [Table 1]

Claims

1. Based on the weight of the composition: a) at least one water-soluble inorganic salt, 1-20% by weight, said inorganic salt being in a dissolved state; b) at least one particulate solid lubricant; c) at least one rheology control agent, 0.1 to 5 wt. %; d) 0.1 to 5% by weight of at least one base; and e) 0.1 to 5 wt. % of at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and zwitterionic surfactants 1. An aqueous lubricating composition comprising: wherein the composition is free of boron and boron compounds; and wherein the weight ratio of b) the at least one solid lubricant to a) the at least one water-soluble inorganic salt [(b):(a)] is from 0.1:1 to 1:

1.

2. Based on the weight of the composition: a) 2 to 20% by weight, preferably 5 to 20% by weight, of said at least one water-soluble inorganic salt; b) said at least one particulate solid lubricant; c) said at least one rheology control agent, 0.1 to 2.5 wt. %, preferably 0.1 to 2 wt. %; d) 0.1 to 2.5% by weight, preferably 0.1 to 2% by weight, of said at least one base; and e) 0.1 to 2.5 wt. %, preferably 0.1 to 2 wt. %, of at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and zwitterionic surfactants.

1. An aqueous lubricating composition comprising:

2. The aqueous lubricating composition of claim 1, further characterized in that the composition is free of boron and boron compounds, and the weight ratio of b) the at least one solid lubricant to a) the at least one water-soluble inorganic salt [(b):(a)] is from 0.1:1 to 1:1, preferably from 0.2:1 to 1:

1.

3. 2. The aqueous lubricating composition of claim 1, comprising 60 to 90 wt. %, preferably 65 to 85 wt. %, more preferably 65 to 80 wt. % water, based on the weight of the composition.

4. 10. The aqueous lubricating composition of claim 1, characterized by a viscosity of 0.005 to 1 Pa·s measured at 25°C using a Brookfield viscometer.

5. 2. The aqueous lubricating composition of claim 1, wherein the total amount of rheology control agent (c) present in the composition is 1 to 10 wt. %, preferably 2 to 8 wt. %, of the total weight of components a) and b).

6. 2. The aqueous lubricating composition of claim 1, having a pH of 7 to 10, preferably 7 to 9.

7. 10. The aqueous lubricating composition of claim 1, wherein component a) comprises a mixture of sodium sulfate, potassium tripolyphosphate, and sodium tripolyphosphate.

8. The or each particulate solid lubricant contained in the composition has a d of less than 5 microns as measured by laser diffraction ５０ 10. The aqueous lubricating composition of claim 1, characterized by a particle size.

9. The component b) is: at least one phosphate selected from the group consisting of zinc phosphate, zinc calcium phosphate, and manganese phosphate; and At least one wax selected from the group consisting of polyethylene wax; oxidized polyethylene wax; polypropylene wax; oxidized polypropylene wax; and copolymer waxes based on ethylene or propylene as the primary monomer. Including, Furthermore, the at least one wax has a number average molecular weight (M) of 400 to 30,000 g / mol, preferably 1000 to 25,000 g / mol. ｎ 10. The aqueous lubricating composition of claim 1, wherein

10. 2. The aqueous lubricating composition of claim 1, wherein the at least one rheology control agent is selected from the group consisting of cellulose derivatives; and polysaccharides.

11. 11. The aqueous lubricating composition of claim 10, wherein component c) comprises carboxymethyl cellulose (CMC) and xanthan gum.

12. d) The aqueous lubricating composition of claim 1, wherein the at least one base is selected from the group consisting of bis(2-(N,N'-dimethylamino)ethyl)ether; bis-(t-butylaminoethyl)ether, 1,2-bis-(t-butylaminoethoxy)ethane; 1,2-bis-(t-butylaminoethoxyethoxy)ethane; bis[2-(isopropylamino)propyl]ether; and 1,2-[2-isopropylamino)propoxy]ethane.

13. 13. The aqueous lubricating composition of claim 12, wherein component d) comprises or consists of bis(2-(N,N'-dimethylamino)ethyl) ether.

14. Use of an aqueous lubricating composition according to any one of claims 1 to 13, or a dried film obtained therefrom, in the plastic cold working of metal substrates.

15. 1. A method for plastically cold working a solid metal substrate by mechanically forcing the solid metal substrate through an opening bounded by at least one solid surface of at least one metalworking tool, said method comprising the steps of: i) applying the aqueous lubricating composition according to any one of claims 1 to 13 to at least one solid surface of the metal substrate, which surface, if uncoated, will come into direct contact with a solid metalworking tool surface during the process; ii) drying the applied aqueous lubricating composition to form a film on the at least one solid surface of the metal substrate; and iii) mechanically forcing the metal substrate formed in step ii) through said opening bounded by at least one metalworking tool surface such that the metal substrate is cold worked. A method comprising: