Patent Description:
In metal machining processes such as cutting and grinding, a metal-working oil is used to improve machining efficiency, prevent abrasion between a workpiece and a tool to machine the work piece, prolong tool life (cool), and remove metal chips. Such metal-working fluids include an oil-based agent (base oil), e.g., mineral oil, animal and vegetable oil, or synthetic oil, water, and a surface-active compound. Metal working fluids containing mineral oil have challenges in the industry as regards being derived from petroleum oil (fossil) and the ability to be emulsified to form stable emulsions.

There exists a need for a metal working fluid which is environmentally friendly and effective to reduce friction caused by removing material from surfaces of the work piece, and dissipate the heat generated by the frictional contact between the tool and the work piece.

In one aspect, a bio-based metal-working fluid concentrate is provided. The metal-working fluid concentrate comprises: a base oil component in an amount of <NUM>-<NUM> wt. %, based on the total weight of the concentrate; an emulsifier selected from any of the conventional anionic, cationic, nonionic or amphoteric surfactants, in an amount of <NUM> to <NUM> wt. %; at least an optional additive selected from saponifiers, pH buffers, preservatives, extreme pressure EP additives, corrosion inhibitors, anti-wear agents, metal deactivators, defoamers, anti-rust agents, deodorants, dyes, fungicides, bacteriocides, antioxidants, emulsion stabilizers, dispersion stabilizers in an amount of <NUM> to <NUM> wt. %; wherein the base oil component contains at least <NUM> wt. % of a decarboxylated rosin acid (DCR) oil based on the total weight of the base oil component. The DCR oil comprises <NUM> to <NUM> wt. % of tricyclic compounds having <NUM>-<NUM> carbon atoms, one or more C=C groups, and m/z (mass/charge) value of <NUM>-<NUM> as measured by GC-FID-MS; an oxygen content of < <NUM>%; and an acid value of < <NUM> KOH/g, as measured using ASTM E28-<NUM>.

In another aspect, a method of preparing a metal surface for subsequent working of the metal to fabricate articles is prepared. The method comprising: diluting a MWF concentrate in water forming a metal-working fluid (MWF) as oil-in-water emulsion, for a water concentration of <NUM>-<NUM>% based on the total weight of the MWF, and apply the oil-in-water emulsion as a substantially continuous layer onto the metal surface to deposit onto the metal surface an ultra-thin film of the metal working fluid. The DCR oil comprises <NUM> to <NUM> wt. % of tricyclic compounds having <NUM>-<NUM> carbon atoms, one or more C=C groups, and m/z (mass/charge) value of <NUM>-<NUM>. The DCR comprises > <NUM> wt. % of tricyclic and polycyclic compounds having <NUM>-<NUM> carbon atoms, amount of tricyclic compounds as reactive double bond DCR (C=C group) in the DCR is < <NUM> wt. %, based on total weight of the DCR, and sum of amounts of tricyclic compounds as aromatics DCR and cycloaliphatic DCR in the DCR is > <NUM> wt. %, based on total weight of the DCR.

The following terms will be used throughout the specification with the following meanings unless specified otherwise.

"At least one of [a group such as A, B, and C]" or "any of [a group such as A, B, and C]," or "selected from [A, B, and C], and combinations thereof' means a single member from the group, more than one member from the group, or a combination of members from the group. For example, at least one of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C; or A, B, and C, or any other all combinations of A, B, and C. In another example, at least one of A and B means A only, B only, as well as A and B.

A list of embodiments presented as "A, B, or C" is to be interpreted as including the embodiments, A only, B only, C only, "A or B," "A or C," "B or C," or "A, B, or C.

"Deionized water" (DI water, DIW or de-ionized water), or demineralized water (DM water), is water that has had almost all its mineral ions removed, such as cations like sodium, calcium, iron, and copper, and anions such as chloride and sulfate.

"Metal-working fluid" may be used interchangeably with MWF, or "metal-working composition," "metal removal fluid," "cutting fluid," "machining fluid," referring to a composition that can be used in industrial metal cutting, metal grinding operations or in the semiconductor industry wherein the shape of the final object, e.g., silicon wafer or machine part, is obtained by with or without the progressive removal of metal or silicon. Metal-working fluids amongst other functions, are used to cool and to lubricate.

"Soluble Oil" refers to a MWF which contain appreciable amounts of water and provided to the end-user as an oil-in-water emulsion containing specialty additives. The oil content of a Soluble Oil MWF concentrate ranges from <NUM>-<NUM>%, with the oil content in the final MWF in application ranges from about <NUM>-<NUM> wt. %, and typically diluted with water at the user's site.

"Semi-synthetic Fluid" refers to a MWF concentrate containing <NUM>-<NUM> wt. % oil and are diluted in water at the user's site.

Density is measured per ASTM D792-<NUM>.

The disclosure relates to a biobased metal-working fluid ("MWF") composition and method for making same, and more particularly MWF with biobased base oils with improved emulsion stability. The biobased base oil is a plant-derived decarboxylated rosin acid ("DCR") liquid product.

Water Component: The metal-working fluid contains an aqueous phase which may be either deionized water (DI water), or hard water, or any combination thereof.

In embodiments and depending on the application, the amount of water in the final MWF (at the application site) ranges from <NUM>-<NUM>%, or <NUM>-<NUM>%, or > <NUM>%, or up to <NUM>%, or up to <NUM>% of the total weight of the final MWF.

Major Component - Decarboxylated Rosin Acid (DCR) as Base Oil: In embodiments, the MWF contains DCR as the only base oil component (<NUM>%), or > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. % of the base oil component. DCR can be either a crude DCR, a distilled or purified DCR (> <NUM>% purity), or mixtures thereof. Crude DCR is almost similar in composition with the distilled DCR, with the heavy fraction (<NUM>-<NUM>%) being removed to improve color, reduce sulfur, etc..

DCR is produced by the decomposition of rosin acids at high temperatures. Rosin acids are normally solid, having a softening point of, e.g., <NUM>- <NUM>. Rosin acid is non-petroleum and plant-derived from gum (from pine trees), wood (from tree stumps), and tall oil (by-product from the paper industry). The rosin acids can be fully or partially decarboxylated, forming decarboxylated rosin acid (DCR or DCR oil).

DCR is mixture of molecules, some of which contain monocarboxylic acids having a general molecular formula, e.g., C<NUM>H<NUM>O<NUM>. In embodiments, DCR is characterized as containing <NUM> - <NUM> wt. % of tricyclic compounds and polycyclic having <NUM> - <NUM> carbon atoms, one or more C=C groups, and m/z (mass/charge) values in the range of <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or > <NUM>, or < <NUM> as measured by GC-FID-MS. m/z is defined as the molecular weight (MW) divided by the charge of the compound, which is ~ <NUM> for DCR.

In embodiments, sum of tricyclic compounds as aromatic and cycloaliphatic in the DCR is > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. % of total weight of the DCR. Aromatic DCR is defined as DCR species having a MW of <NUM> or <NUM>, and cycloaliphatic DCR is defined as DCR species having a MW of <NUM> or <NUM>.

In embodiments, the amount of cycloaliphatic DCR is > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. %, based on the total weight of the DCR.

In embodiments, total amount of tricyclic compounds as reactive double bond (C=C group) is < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. % of total weight of the DCR. Reactive C=C group is defined as DCR species having a MW of <NUM> and <NUM>.

In embodiments, the DCR is characterized as having an oxygen content of < <NUM>%, or < <NUM>%, or < <NUM>%, or <NUM>-<NUM>%. Oxygen content (in %) in the DCR is calculated as the oxygen to carbon ratio, or the sum of oxygen atoms present divided by sum of carbon atoms present, with the number of oxygen and carbon atoms being obtained from elemental analyses.

In embodiments, the DCR has a density of <NUM> - <NUM>/cm<NUM>, <NUM> - <NUM>/cm<NUM>, or <NUM> - <NUM>/cm<NUM>, or <NUM> - <NUM>/cm<NUM>, or <NUM> - <NUM>/cm<NUM>, > <NUM>/cm<NUM>, or < <NUM>/cm<NUM> at <NUM>.

The DCR has a low acid value (carboxylic acid content) than the rosin acid. In embodiments, the DCR has the acid value of < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or < <NUM> KOH/g, or <NUM> - <NUM> KOH/g, or <NUM> - <NUM> KOH/g , or <NUM> - <NUM> KOH/g, as measured using ASTM E28-<NUM>.

In embodiments, the DCR has an aromatic content of <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or > <NUM> wt. %, or < <NUM> wt. %, based on the total weight of the DCR, according to ASTM D2140.

In embodiments, the DCR has a naphthenic content of <NUM> - <NUM> wt. %, <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or > <NUM> wt. %, or < <NUM> wt. %, based on the total weight of the DCR, according to ASTM D2140.

In embodiments, the DCR has a paraffinic content of <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or <NUM> - <NUM> wt. %, or > <NUM> wt. %, or < <NUM> wt. %, based on the total weight of the DCR, according to ASTM D2140.

In embodiments, the DCR is characterized as having viscosities comparable to those of petrochemical base oils, due in part to its relatively high molecular weights, for example, a viscosity of <NUM> - <NUM> cSt, or <NUM> - <NUM> cSt, or <NUM> - <NUM> cSt, or <NUM> - <NUM> cSt, or <NUM> - <NUM> cSt, or > <NUM> cSt, or < <NUM> cSt, according to ASTM D-<NUM>, measured at <NUM>.

In embodiments, the DCR has an aniline point of <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or < <NUM>, or > <NUM>, according to ASTM D611.

In embodiments, the DCR has a pour point of -<NUM> to +<NUM>, -<NUM> to +<NUM>, or -<NUM> to +<NUM>, or > -<NUM>, or < +<NUM>, according to ASTM D97.

In embodiments, the DCR has a flash point of <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or > <NUM>, or < <NUM>, or < <NUM>, according to ASTM D92.

In embodiments, the DCR has a boiling point of <NUM> - <NUM>, or > <NUM>, or < <NUM>, measured according to D2887.

In embodiments, the DCR has a Gardner Color of <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, or <NUM> - <NUM>, > <NUM>, or < <NUM>, or < <NUM>, according to ASTM D6166.

In embodiments, the DCR has a sulfur content of < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or <NUM>-<NUM> ppm, or < <NUM> ppm, or < <NUM> ppm, based on total weight of the DCR, measured according to ASTM D5453.

In embodiments, the DCR has a VOC of < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, or < <NUM> wt. %, < <NUM> wt. %, < <NUM> wt. %, < <NUM> wt. %, < <NUM> wt. %, or < <NUM> wt. %, < <NUM> wt. %, < <NUM> wt. %, or < <NUM> wt. %, < <NUM> wt. %, or < <NUM> wt. %, based on total weight of the DCR. The VOC of the DCR is measured according to the EPA (Environmental Protection Agency) method <NUM> or equivalent, by summing the % by weight contribution from all VOCs present in the product at <NUM>% or more.

In embodiments of Semi-synthetic Fluid MWF, the DCR oil amount ranges from <NUM>-<NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. %, or > <NUM> wt. %, or < <NUM> wt. % of the total weight of the MWF concentrate.

In embodiments for Soluble Oil MWF, the amount of DCR ranges from <NUM>-<NUM> wt. %, or > <NUM>% wt. %, or > <NUM> wt. %, or > <NUM> wt. %, or < <NUM> wt. % of the total weight of the MWF concentrate.

Optional Base Oil Component: In some embodiments, a small amount of a (different) oil can be used in addition to the DCR as the base oil component.

In embodiments, the additional base oil is selected from Group I and / or Group II base oils, e.g., paraffin base crude oil, middle crude oil, or naphthenic base crude oil; vegetable oils (e.g., soybean oil, etc.), short and branched chain esters derived from fats and oils (e.g., methyl ester for soybean, isopropyl oleate, trimethylolpropane oleate, etc.), and refined oils obtained by refining these distillates.

The amount of an additional base oil (other than the DCR), if used, is less than <NUM>% of the total amount of base oil. In embodiments of Semisynthetic Fluid, the amount of additional base oil used ranges from <NUM> to <NUM>%, or < <NUM>%, or < <NUM>% of the total weight of the MWF. In embodiments for Soluble Oil, the amount of additional base oil, if used, ranges from <NUM>-<NUM> wt. %, or < <NUM>%, or < <NUM>%, or < <NUM>% of the total weight of the MWF concentrate.

In embodiments, the additional base oil component is Group I base oil, at a weight ratio of DCR : Group I base oil ranging from <NUM>:<NUM> to <NUM>:<NUM> (as total weight of base oil).

Emulsifier Component: The MWF further comprises at least an emulsifier, and preferably two or more emulsifiers (e.g., an emulsifier and a co-emulsifier), which can be the same or different types. Choices of emulsifiers depend on the amount of water, the amount and type of the oil component used. Emulsifiers are selected from any of the conventional anionic, cationic, nonionic, or amphoteric surfactants.

In embodiments, the emulsifier component is selected from amphoteric compounds. Examples include alkyl-<NUM>-iminodipropionate; alkyl-<NUM>-amino-propionate; fatty imidazolines and betaines, more specifically 1coco-<NUM>-hydroxyethyl-<NUM>-carboxymethyl imidazoline; dodecyl-<NUM>-alanine; N-dodecyl-N, N-dimethyl amino acetic acid; <NUM>-trimethyl amino lauric acid inner salts; and the like.

In embodiments, the emulsifier component is selected from nonionic surfactants such as ethylene oxide adducts of alcohols, polyols, phenols, carboxylic acids, and carboxylic acid esters such as ethylene oxide adducts of oleyl alcohol, nonyl phenol, glycerol, sorbitol, mannitol, pentaerythritol, sorbitan monolaurate, glycerol monooleate, pentaerythritol monostearate, oleic acid, stearic acid, and the like.

In embodiments, the emulsifier component is selected from cationic compounds include cetyl pyridinium bromide, hexadecyl morpholinium chloride, dilauryl triethylene tetramine diacetate, didodecylamine lactate, <NUM>-amino-<NUM>-heptadecenyl imidazoline acetate, cetyl amine acetate, oleylamine acetate, ethoxylated tallow, coco, stearyl, oleyl or soya amine, and the like. Useful anionic compounds include alkali metal salts of petroleum sulfonic acids, alkali metal salts of fatty acids, amine and ammonium soaps of fatty acids, alkali metal dialkyl sulfosuccinates, sulfated oils, sulfonated oils, alkali metal alkyl sulfates, and the like.

In embodiments, the emulsifiers are oil-soluble emulsifiers such as such as organic sulfonates, esters of fatty acids, polyoxyethylene acids, alcohols and alkanolamides, and alkanolamines, the latter generally being preferred. Examples include monoethanolamine, diethanolamine, triethanolamine, or isopropanolamine.

In embodiments, an emulsifier which is <NUM>-<NUM>% soluble in water is used, e.g., a rosin acid ester. In an embodiment, a distilled tall oil (DTO) or a tall oil fatty acid (TOFA) is used and the main emulsifier, or a co-emulsifier in conjunction with another emulsifier (e.g., a sulfonate).

The amount of emulsifier ranges from <NUM> to <NUM>%, or <NUM>% to <NUM>%, or at least <NUM>% of the total weight of the MWF concentrate.

Optional Components: The metal working fluid optionally comprises one or more components selected from saponifiers or (pH) buffers, preservatives, extreme pressure (EP) additives or anti-wear additives, corrosion inhibitors, anti-wear agents, metal deactivators, defoamers, anti-rust agents, deodorants, dyes, fungicides, bacteriocides, antioxidants, emulsion or dispersion stabilizers and the like, deodorants, dyes, fungicides, bacteriocides.

Examples of saponifiers / buffers include alkanolamines, e.g., primary, secondary and tertiary, aminomethylpropanol (AMP-<NUM>), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicylclohexylamine (DCHA), diethanolamine (DEA), butyldiethanolamine (NBDEA), triethanolamine (TEA), metal alkali hydroxides, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonatetriethanolamine and ethylenediaminetetraacetic acid.

Examples of corrosion inhibitors include but are not limited to organic amines, metallic salts of organic sulfonates, petroleum oxidates, organic diamines, or-ganic amine condensates of fatty alcohols, and substituted imidazolines.

Examples of anti-wear additives (AW, lubricity improvers) include organic acids. Examples of such organic acids include caprylic acid, pelargonic acid, isononanoic acid, capric acid, lauric acid, stearic acid, oleic acid, benzoic acid, p-tert-butylbenzoic acid, adipic acid, suberic acid, sebacic acid, azelaic acid, and dodecandioic acid.

In embodiments, the MWF includes at least an extreme pressure (EP)/ coupling agent selected from zinc dithiophosphate (ZDP), zinc dialkyl dithio phosphate (ZDDP), tricresyl phosphate (TCP), Halocarbons (chlorinated paraffins), Glycerol mono oleate, Stearic acid, nonionic surfactant include ethers such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether; esters such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene fatty acid ester; and conventional coupling agents such as volatile alcohols such as sec-butanol, butyl oxitol or cyclohexanol.

In embodiments, depending on the optional additives, the amount ranges from <NUM> to <NUM> wt. %, or <<NUM> wt. %, or > <NUM> wt. %, or < <NUM> wt. %, or <<NUM> wt. % of the total weight of the MWF concentrate.

Method for Making / Applications: Depending on the base oil employed (<NUM>% DCR, or a mix of DCR and at least a different base oil), the components can be mixed at the same time, or in certain sequences, forming a concentrate. In embodiments, additives such as corrosion inhibitors and emulsifiers are first missed, prior to the addition of additives such as the saponifier, and then the buffer.

In use, the MWF is subsequently produced by dispersing the concentrate with water, e.g., using a high shear mixer for use metal machining processes such as cutting, grinding, punching, polishing, deep drawing, drawing, and rolling, providing excellent lubricity for machining a so-called hard-to-work material.

Properties: Metal-working fluids prepared from the concentrate with DCR (or a mix with DCR and a different base oil) as a base oil component is characterized as providing same or better performance compared to MWF prepared solely from mineral oils, e.g., Group I or Group II oil.

In embodiments with a base oil component containing at least <NUM>% DCR (based on the amount of DCR in total amount of base oil component), the MWF as prepared shows excellent stability, even after <NUM> days at <NUM>. In high frequency reciprocating rig (HFRR) tests, the MWF showed comparable film thickness and friction coefficient versus the corresponding MWF with naphthenic oil water in oil emulsion. The oil-in-water MWF fluid also shows minimal foam formation, of less than <NUM> per foam test (as explained below).

Examples: The following tests were conducted on the samples in the examples:.

Rosin oils: Rosin oils were prepared by experimental procedure known in the art as shown below for comparative examples. The nomenclature xx as in "AN-<NUM>," "AN-<NUM>," etc., refers to the acid number of the (crude) rosin oil sample. PTSA refers to p-toluene sulfonic acid, and PTSA/S refers to experiments with PTSA with the inclusion of sulfur.

Rosin oil AN-<NUM> (PTSA/S): Rosin acid was heated to <NUM>, in a round bottom flask and then <NUM> wt. % sulfur was charged. The temperature was increased and remained at <NUM> after sulfur charge. After <NUM> hrs. reaction mixture was charged with <NUM> wt. % of PTSA and the temperature increased to <NUM>. The reaction mixture was kept at <NUM> for <NUM> hours until the acid number of <NUM> KOH/g was obtained.

Rosin oil AN-<NUM> (PTSA/S): AN <NUM> was obtained in the same manner as AN-<NUM>, except that the reaction mixture was held at <NUM> for <NUM> hour for an acid number of <NUM> KOH/g.

Rosin Oil AN-<NUM> (Thermal): The experiment was without any catalyst, e.g., PTSA/S. Rosin acid was heated to <NUM> at <NUM>/hr. and reaction was held at <NUM> for <NUM> hours until reaching <NUM> KOH/g.

Other Rosin Oils: The above experiments were repeated but with different reaction time periods for rosin oil samples with different acid numbers, e.g., AN-<NUM> (PTSA/S), AN-<NUM> (PTSA/S), AN-<NUM> (Thermal), and with a different catalyst (hydrophosphorous) for AN-<NUM>. These comparable rosin oils are used in Examples 5A-5E.

Distillate Examples: Some of the prior art rosin oil samples and DCR samples were refined to obtained distillate samples. Properties of the crude DCR are below in Table 2A, and properties of the distilled DCR are shown in Table 2B below.

Examples 1A -1F Soluble Oil MWF in DI Water: MWF formulations were produced from different concentrates with components according to Table <NUM>, with different base oil replacing the naphthenic base oil in Table <NUM>. MWF formulations were made by dispersing <NUM> grams of each concentrate into <NUM> grams of DI (deionized) water for each example. The differences in the examples being the base oil component(s) and proportions as indicated in Table <NUM>, with some examples having DCR (with acid number of ~ <NUM> KOH/g) and mineral oil base components. Table <NUM> also shows with results of the tests for stability, particle size, foaming tendency, lubricity, and corrosion.

Examples 2A - 2F - Semi-Synthetic MWF in DI Water: MWF formulations were produced from concentrates with the components according to Table <NUM>, with different base oil as the replacement. MWF formulations were made by dispersing <NUM> grams of the concentrate into <NUM> grams of DI (deionized) water for each example. As with the above examples, the differences in the examples being the base oil component(s) and proportions as indicated in Table <NUM>, with some examples having DCR (with acid number of ~ <NUM> KOH/g) and mineral oil base components. Table <NUM> also shows with results of the tests for stability, particle size, foaming tendency, lubricity, and corrosion.

Examples 3A -3F Soluble Oil MWF in Hard Water: Examples 1A-1F with soluble oil concentrate formulations were repeated, but the concentrates were dispersed in hard water (<NUM> ppm of calcium chloride in DI water), instead of just DI. Table <NUM> shows test results for stability, particle size, foaming tendency, lubricity, and corrosion.

Examples 4A - 4B: MWF formulations were produced from different concentrates with components according to Table <NUM>, with different rosin oils replacing the naphthenic base oil in Table <NUM>. MWF formulations were made by dispersing <NUM> grams of each concentrate into <NUM> grams of hard water for each example. Table <NUM> shows with results of the tests for stability, particle size, foaming tendency, lubricity, and corrosion.

Examples 5A - 5E: MWF formulations were produced from different concentrates with components according to Table <NUM>, with different rosin oil and distillates replacing the naphthenic base oil in Table <NUM>. MWF formulations were made by dispersing <NUM> grams of each concentrate into <NUM> grams of hard water for each example. Table <NUM> shows results of the tests for stability, particle size, foaming tendency, lubricity, and corrosion.

Examples 6A - 6E: MWF formulations were produced from different concentrates with components according to Table <NUM>, with olive oil, methyl oleate and isopropyl oleate replacing the naphthenic base oil in Table <NUM>, with <NUM> grams of each concentrate into <NUM> grams of hard water. Table <NUM> shows with results of the tests for stability, particle size, foaming tendency, lubricity, and corrosion.

Examples 7A -7F Semi-Synthetic MWF in Hard Water: Examples 2A-2F with semi-synthetic concentrate formulations were repeated, but the concentrates were dispersed in hard water (<NUM> ppm of calcium chloride in DI water), instead of just DI. Table <NUM> shows test results for stability, particle size, foaming tendency, lubricity, and corrosion.

As illustrated, DCR can be substituted for all or part of mineral oils, e.g., Group I or Group II. A Group II oil which does not produce a stable product when used in the same formulation can be supplemented with <NUM>% DCR to produce a stable product. Substituting <NUM>% of the naphthenic oil to the paraffinic oil does not provide the same remediation. Although there are some differences seen when formulating with hard water versus DI water, the variations between the traditional oils and DCR are minimal, mainly as regards long term stability at <NUM>.

Claim 1:
A metal-working fluid concentrate for use as an oil-in-water emulsion, comprising:
a base oil component in an amount of <NUM>-<NUM> wt. %, based on the total weight of the concentrate.
an emulsifier selected from any of the conventional anionic, cationic, nonionic, or amphoteric surfactants, in an amount of <NUM> to <NUM> wt. %.
at least an additive selected from saponifiers, pH buffers, preservatives, extreme pressure EP additives, corrosion inhibitors, anti-wear agents, metal deactivators, defoamers, anti-rust agents, deodorants, dyes, fungicides, bacteriocides, antioxidants, emulsion stabilizers, dispersion stabilizers in an amount of <NUM> to <NUM> wt. %.
wherein the base oil component contains at least <NUM>% by weight of a decarboxylated rosin acid (DCR) based on the total weight of the base oil component, and remainder being oil selected from naphthenic, paraffin, bio-based oil and mixtures thereof, and
wherein the DCR has:
a m/z (mass/charge) of <NUM>-<NUM> as measured by GC-FID-MS,
an oxygen content of < <NUM>% as obtained from elemental analysis,
an acid value of < <NUM> KOH/g as measured according to ASTM E28-<NUM>; and
wherein the DCR comprises:
> <NUM> % by weight as tricyclic and polycyclic compounds having <NUM>-<NUM> carbon atoms as measured by GC-FID-MS,
> <NUM> % by weight of tricyclic compounds as aromatic and cycloaliphatic as measured by GC-FID-MS,
< <NUM> % by weight of tricyclic compounds as reactive double bond (C=C group) as measured by GC-FID-MS.