Metalworking fluid composition and method of manufacture

Abstract

To provide a metal-working fluid which is environmentally friendly and is effective to reduce friction caused by removing material from a surface of a work piece and dissipate heat generated by frictional contact between a tool and the work piece.SOLUTION: The disclosure relates to a biobased metal-working fluid (MWF) composition and a method for producing the same, and more particularly a metal-working fluid with biobased lubricants with improved emulsion stability. At least 50 wt.% of base oil components in an MWF concentrate is a plant-derived liquid decarboxylated rosin acid oil ("DCR"). The DCR comprises 50 to 100 wt.% of tricyclic compounds having: 18-20 carbon atoms; one or more C=C groups; an m / z (mass / charge) value of 220-280 as measured by GC-FID-MS; an oxygen content of less than 5%; and an acid value of less than 50 mg KOH / g as measured using ASTM E28-18. The resulting MWF is characterized as having comparable or good performance compared to an MWF containing only mineral oil (e.g., Group I or Group II).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to bio-based metalworking fluid (MWF) compositions and methods for making same, and more particularly to metalworking fluids having improved emulsion stability and including decarboxylated rosin acids as lubricants. [Background technology]

[0002] In metalworking processes such as cutting and grinding, metalworking fluids are used to improve processing efficiency, prevent friction between the workpiece and the tool used to process the workpiece, extend the tool's (net) life, and remove metal debris. Such metalworking fluids include an oily substance (base oil), such as mineral oil, animal oil, vegetable oil, or synthetic oil, water, and a surface-active compound. Metalworking fluids containing mineral oil present industrial challenges due to their petroleum (fossil) origin and their ability to emulsify to form stable emulsions. Summary of the Invention [Problem to be solved by the invention]

[0003] There is a need for metalworking fluids that are environmentally friendly, reduce friction caused by removal of material from the surface of a workpiece, and are effective in dissipating heat generated by frictional contact between the tool and workpiece. [Means for solving the problem]

[0004] In one embodiment, a bio-based metalworking fluid concentrate is provided, comprising a base oil component in an amount of 5 to 90 wt %, based on the total weight of the concentrate, an emulsifier selected from typical anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants in an amount of 0.1 to 15 wt %, and at least one optional additive selected from saponifying agents, pH buffers, preservatives, extreme pressure EP additives, corrosion inhibitors, antiwear agents, metal deactivators, defoamers, rust inhibitors, deodorizers, dyes, mildew inhibitors, bactericides, antioxidants, emulsion stabilizers, and dispersion stabilizers in an amount of 0.1 to 15 wt %, based on the total weight of the base oil component, wherein the base oil component contains at least 50 wt % decarboxylated rosin acid (DCR) oil, based on the total weight of the base oil component. DCR oils contain 50-100% by weight of tricyclic compounds having 18-20 carbon atoms, one or more C=C groups, an m / z (mass / charge) value of 220-280 as measured by GC-FID-MS, an oxygen content of less than 5%, and an acid number of less than 50 mg KOH / g as measured using ASTM E28-18.

[0005] In another aspect, a method for preparing a metal surface for subsequent metalworking to produce a product is provided. The method includes diluting an MWF concentrate with water to form a metalworking fluid (MWF) as an oil-in-water emulsion, with the water concentration being 80-99% based on the total weight of the MWF, and applying the oil-in-water emulsion as a substantially continuous layer onto the metal surface to deposit an ultra-thin film of the metalworking fluid on the metal surface. The DCR oil contains 50-100% by weight of a tricyclic compound having 18-20 carbon atoms, one or more C=C groups, and an m / z (mass / charge) value of 220-280. The DCR contains more than 50% by weight of tricyclic and polycyclic compounds having 18 to 20 carbon atoms, the amount of tricyclic compounds as reactive double bond DCRs (C=C groups) in the DCR is less than 45% by weight based on the total weight of the DCR, and the sum of the amounts of tricyclic compounds as aromatic DCRs and alicyclic DCRs in the DCR is more than 55% based on the total weight of the DCR. DETAILED DESCRIPTION OF THE INVENTION

[0006] The following terms are used throughout the specification and have the following meanings unless otherwise indicated.

[0007] "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 of the group, more than one member of the group, or a combination of members of 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 all other combinations of A, B, and C. In another example, at least one of A and B means A only, B only, and A and B.

[0008] A list of embodiments presented as "A, B, or C" should be interpreted as including the embodiments of A only, B only, C only, "A or B," "A or C," "B or C," or "A, B, or C."

[0009] "Deionized water" (DI water, DIW or deionized water) or demineralized water (DM water) is water from which nearly all inorganic ions have been removed, including cations such as sodium, calcium, iron and copper, and anions such as chloride and sulfide.

[0010] "Metalworking fluid", which may be used interchangeably with MWF, or "metalworking composition", "metal removal fluid", "cutting fluid" or "working fluid", refers to a composition that can be used in industrial metal cutting or metal milling processes, or in the semiconductor industry, where the final object, e.g., silicon wafer or machine part shape, is obtained with or without the gradual removal of metal or silicon. Metalworking fluids are used for cooling and lubrication, among other functions.

[0011] "Solubilized oil" refers to MWFs that contain a significant amount of water and are provided to the end user as oil-in-water with special additives. The oil content in the solubilized oil MWF concentrate ranges from 40-90%, and the oil content in the final MWF to be applied ranges from about 5-10% by weight, and is typically diluted with water at the user's location.

[0012] "Semi-synthetic fluid" refers to an MWF concentrate containing 5-40% oil by weight, which is diluted with water at the user's location.

[0013] Weight percent refers to weight concentration.

[0014] Density is measured according to ASTM D792-13.

[0015] The present disclosure relates to bio-based metalworking fluid ("MWF") compositions and methods for making the same, and more particularly to MWFs having improved emulsion stability and including a bio-based base oil, which is a plant-derived decarboxylated rosin acid ("DCR") liquid product.

[0016] Water Component: The metalworking fluid includes a water phase that may be deionized water (DI water), or hard water, or any combination thereof.

[0017] In some embodiments, and depending on the application, the amount of water in the final MWF (at the point of use) is 80-99%, or 85-92%, or more than 90%, or 95% or less, or 99% or less of the total weight of the final MWF.

[0018] Decarboxylated Rosin Acid (DCR) as the Main Component—Base Oil: In some embodiments, the MWF contains DCR as the sole base oil component (100%), or greater than 50 wt. %, greater than 60 wt. %, or greater than 70 wt. % of the base oil component. The DCR can be crude DCR, distilled DCR, refined DCR (greater than 90% pure), or a mixture thereof. Crude DCR is similar in composition to distilled DCR, where the heavy ends (10-15%) have been removed, such as to improve color and reduce sulfur.

[0019] DCR is produced by decomposing rosin acid at high temperatures. Rosin acid is typically a solid with a softening point, e.g., 65-85°C. Rosin acid is not derived from petroleum but from plant sources such as resin (from pine trees), wood (from stumps), and tall oil (a papermaking by-product). Rosin acid can be fully or partially decarboxylated to form decarboxylated rosin acid (DCR or DCR oil).

[0020] DCR is a type of 20 H 30 DCR is a mixture of molecules containing monocarboxylic acids with the general molecular formula of O. In some embodiments, DCR is characterized as containing 40-100% by weight of tricyclic and polycyclic compounds containing 18-20 carbon atoms, one or more C=C groups, and having m / z (mass / charge) values ​​of 220-280, 230-270, 234-262, or 235-265, or greater than 230, or less than 265, as measured by GC-FID-MS. m / z is defined as the molecular weight (MW) of the compound divided by its charge, which for DCR is approximately 1.

[0021] In some embodiments, the sum of the aromatic and alicyclic tricyclic compounds in the DCR is greater than 50 wt%, or greater than 55 wt%, or greater than 60 wt%, or greater than 74 wt%, or greater than 90 wt% of the total weight of the DCR. Aromatic DCRs are defined as DCR species with a MW of 252 or 256, and alicyclic DCRs are defined as DCR species with a MW of 260 or 262.

[0022] In some embodiments, the amount of cycloaliphatic DCR is greater than 30 wt%, or greater than 40 wt%, or greater than 50 wt%, or greater than 80 wt%, based on the total weight of the DCR.

[0023] In some embodiments, the total amount of tricyclic compounds as reactive double bonds (C=C groups) is less than 45 wt%, or less than 40 wt%, or less than 30 wt%, or less than 10 wt%, based on the total weight of the DCR. Reactive C=C groups are defined as DCR species with MWs of 254 and 258.

[0024] In some embodiments, the DCR is characterized as having an oxygen content of less than 5%, or less than 3%, or less than 2%, or 0-1%. The % oxygen content in the DCR is calculated as the ratio of oxygen to carbon, or the total oxygen atoms present divided by the total carbon atoms present, where the number of oxygen and carbon atoms is obtained by elemental analysis.

[0025] In some embodiments, the DCR has a density at 20°C of 0.9 to 1.0 g / cm 3 , or 0.91 to 0.99 g / cm 3 , or 0.92 to 0.98 g / cm 3 , or 0.93 to 0.97 g / cm 3 , or 0.94 to 0.96 g / cm 3 or 0.9 g / cm 3 or more than 1.1 g / cm 3 is less than.

[0026] DCR has a lower acid number (carboxylic acid content) than rosin acid. In some embodiments, the DCR has an acid number, as measured using ASTM 28-18, of less than 50 mg KOH / g, or less than 45 mg KOH / g, or less than 40 mg KOH / g, or less than 35 mg KOH / g, or less than 30 mg KOH / g, or less than 25 mg KOH / g, or less than 20 mg KOH / g, or less than 15 mg KOH / g, or less than 5 mg KOH / g, or between 2 and 30 mg KOH / g, or between 4 and 25 mg KOH / g, or between 5 and 20 mg KOH / g.

[0027] In some embodiments, the DCR has an aromatics content according to ASTM D2140 of 30-60 wt%, or 32-56 wt%, or 35-54 wt%, or 38-52 wt%, or 40-50 wt%, or greater than 30 wt%, or less than 45 wt%, based on the total weight of the DCR.

[0028] In some embodiments, the DCR has a naphthenic content according to ASTM D2140 of 40-60 wt%, or 42-58 wt%, or 45-55 wt%, or 42-52 wt%, or greater than 45 wt%, or less than 55 wt%, based on the total weight of the DCR.

[0029] In some embodiments, the DCR has a paraffinic content according to ASTM D2140 of 20-35 wt%, or 22-34 wt%, or 24-32 wt%, or 26-30 wt%, or greater than 22 wt%, or less than 32 wt%, based on the total weight of the DCR.

[0030] In some embodiments, due in part to its relatively high molecular weight, the DCR has a viscosity comparable to petrochemical base oils, e.g., a viscosity of 20-50 cSt, or 22-48 cSt, or 25-45 cSt, or 28-42 cSt, or 30-40 cSt, or greater than 28 cSt, or less than 45 cSt, measured at 40°C by ASTM D-445.

[0031] In some embodiments, the DCR is an aniline point according to ASTM D611 of 5 to 40°C, or 10 to 25°C, or 13 to 29°C, or less than 25°C, or greater than 8°C.

[0032] In some embodiments, the DCR has a pour point according to ASTM D97 of -30 to +10°C, or -28 to +8°C, or -25 to +5°C, or greater than -25°C, or less than +5°C.

[0033] In some embodiments, the DCR has a flash point according to ASTM D92 of 140-160°C, or 142-158°C, or 144-156°C, or 146-154°C, or greater than 146°C, or less than 154°C, or less than 160°C.

[0034] In some embodiments, the DCR has a boiling point of 235-390°C, or greater than 230°C, or less than 400°C, as measured according to D2887.

[0035] In some embodiments, the DCR is a Gardner color scale according to ASTM D6166 of 1.0 to 3.0, or 1.1 to 2.9, or 1.2 to 2.8, or 1.3 to 2.7, or 1.4 to 2.6, or 1.5 to 2.5, or greater than 1.2, or less than 2.4, or less than 3.0.

[0036] In some embodiments, the DCR has a sulfur content, measured according to ASTM D5453, of less than 0.05 wt.%, or less than 0.04 wt.%, or less than 0.03 wt.%, or less than 0.02 wt.%, or less than 0.01 wt.%, or less than 0.001 wt.%, or 40-200 ppm, or less than 500 ppm, or less than 100 ppm, based on the total weight of the DCR.

[0037] In some embodiments, the DCR has less than 5 wt. % VOC, or less than 4.75 wt. %, or less than 4.5 wt. %, or less than 4.25 wt. %, or less than 4.0 wt. %, or less than 3.75 wt. %, or less than 3.5 wt. %, or less than 3.25 wt. %, or less than 3.0 wt. %, or less than 2.75 wt. %, or less than 2.5 wt. %, or less than 2.25 wt. %, or less than 2.0 wt. %, or less than 1.5 wt. %, or less than 1.0 wt. %, or less than 0.5 wt. % VOC of the DCR is measured by EPA Method 24 or its equivalent by adding up the weight percent contributions of all VOCs present in the product at 0.01% or greater.

[0038] In some embodiments of the semi-synthetic liquid MWF, the amount of DCR oil ranges from 5 to 40 wt. % of the total weight of the MWF concentrate, or greater than 5 wt. %, or greater than 30 wt. %, or greater than 35 wt. %, or less than 45 wt. %.

[0039] In some embodiments for solubilized oil MWFs, the amount of DCR ranges from 40 to 90 wt. % of the total weight of the MWF concentrate, or greater than 55 wt. %, or greater than 60 wt. %, or greater than 65 wt. %, or less than 85 wt. %.

[0040] Optional Base Oil Component: In some embodiments, a small amount of a (different) oil can be used in addition to DCR as the base oil component.

[0041] In some embodiments, the additional base oil is selected from Group I and / or Group II base oils, such as paraffinic, intermediate, or naphthenic crude oils, vegetable oils (such as soybean oil), short-branched esters derived from fats and oils (such as the methyl esters of soybean, isopropyl oleate, and trimethylolpropane oleate), and refined oils obtained by refining distillates thereof.

[0042] If additional base oil (other than DCR) is used, the amount is less than 50% of the total amount of base oil. In some embodiments of semi-synthetic fluids, the amount of additional base oil used ranges from 2 to 25%, or less than 20%, or less than 10% of the total weight of the MWF. In some embodiments of solubilizing oils, if additional base oil is used, the amount ranges from 20 to 45% by weight of the total weight of the MWF concentrate, or less than 40%, or less than 30%, or less than 20%.

[0043] In some embodiments, the additional base oil component is a Group I base oil having a weight ratio of DCR:Group I base oil (as total weight of base oil) ranging from 50:50 to 90:10.

[0044] Emulsifier component: The MWF further comprises at least one emulsifier, preferably two or more emulsifiers (e.g., an emulsifier and a co-emulsifier), which may be the same or different. The choice of emulsifier depends on the amount of water and the amount and type of oil component used. The emulsifier is selected from any of the typical anionic surfactants, cationic surfactants, nonionic surfactants, or amphoteric surfactants.

[0045] In some embodiments, the emulsifier component is selected from amphoteric compounds, such as alkyl-3-iminodipropionates, alkyl-3-amino-propionates, fatty imidazolines and betaines, more specifically 1-coco-5-hydroxyethyl-5-carboxymethylimidazoline, dodecyl-3-alanine, N-dodecyl-N,N-dimethylaminoacetic acid, and 2-trimethylaminolauric acid inner salt.

[0046] In some embodiments, the emulsifier composition is selected from nonionic surfactants such as ethylene oxide adducts of alcohols, polyols, phenols, carboxylic acids and carboxylic acid esters, etc., such as oleyl alcohol, nonylphenol, glycerol, sorbitol, mannitol, pentaerythritol, sorbitan monolaurate, glycerol monooleate, pentaerythritol monostearate, ethylene oxide adducts of oleic acid and stearic acid, etc.

[0047] In some embodiments, the emulsifier composition is selected from cationic compounds including cetylpyridinium bromide, hexadecylmorpholinium chloride, dilauryltriethylenetetramine diacetate, didodecylamine lactate, 1-amino-2-heptadecenylimidazoline acetate, cetylamine acetate, oleylamine acetate, and ethoxylated tallow, coconut, stearyl, oleyl, or soy amines, etc. 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, and alkali metal alkyl sulfates, etc.

[0048] In some embodiments, the emulsifier is an oil-soluble emulsifier 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.

[0049] In some embodiments, emulsifiers that are 50-100% soluble in water, such as rosin acid esters, are used. In one embodiment, distilled tall oil (DTO) or tall oil fatty acid (TOFA) is used as a primary emulsifier or as a co-emulsifier in combination with other emulsifiers (e.g., sulfonates).

[0050] The amount of emulsifier ranges from 0.1 to 15%, or from 0.3% to 12%, or at least 10% of the total weight of the MWF concentrate.

[0051] Optional Ingredients: The metalworking fluid optionally comprises one or more ingredients selected from saponifying agents or (pH) buffering agents, preservatives, extreme pressure (EP) or antiwear additives, corrosion inhibitors, antiwear agents, metal deactivators, defoamers, rust inhibitors, deodorizers, dyes, mildew inhibitors, bactericides, antioxidants, emulsion or dispersion stabilizers and the like, deodorizers, dyes, mildew inhibitors, bactericides.

[0052] Examples of saponifying agents / buffering agents include alkanolamines such as primary, secondary and tertiary alkanolamines, aminomethylpropanol (AMP-95), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicyclohexylamine (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 bicarbonate triethanolamine, and ethylenediaminetetraacetic acid.

[0053] Examples of corrosion inhibitors include, but are not limited to, organic amines, metal salts of organic sulfonates, petroleum oxidates, organic diamines, organic amine condensates of fatty alcohols, and substituted imidazolines.

[0054] Examples of antiwear agents (AW, lubricity improvers) include organic acids such as caprylic acid, pelagonic 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 dodecanedioic acid.

[0055] In some embodiments, the MWF comprises at least one extreme pressure (EP) / coupling agent selected from typical coupling agents such as zinc dithiophosphate (ZDP), zinc dialkyldithiophosphate (ZDDP), triglyceride phosphate (TCP), halocarbons (chlorinated paraffins), glycerol monooleate, stearic acid, nonionic surfactants including ethers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers, esters such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and polyoxyethylene fatty acid esters, and volatile alcohols such as sec-butanol, butyloxytol, or cyclohexanol.

[0056] In some embodiments, the amount is 0.1-15 wt. %, or less than 10 wt. %, or more than 0.5 wt. %, or less than 5 wt. %, or less than 2 wt. % of the total weight of the MWF concentrate, depending on optional additives.

[0057] Method of Preparation / Use: Depending on the base oil employed (100% DCR or a mixture of DCR and at least one different base oil), the components can be mixed simultaneously or in a specific order to form the concentrate. In some embodiments, additives such as corrosion inhibitors and emulsifiers are mixed first, followed by buffers, before the addition of additives such as saponifiers.

[0058] In use, the concentrate is then dispersed with water using a high shear mixer used in metalworking processes such as cutting, grinding, punching, grinding, deep drawing, drawing and rolling to produce a MWF that provides excellent lubrication for processing so-called difficult-to-process materials.

[0059] Properties: Metalworking fluids made from concentrates with DCR (or a mixture of DCR and a different base oil) as the base oil component are characterized as exhibiting equivalent or better performance than MWFs made solely from mineral oils, e.g., Group I or Group II oils.

[0060] In embodiments with a base oil component containing at least 50% DCR (based on the amount of DCR in the total base oil component), the resulting MWFs exhibit excellent stability even after 28 days at 60°C. In high frequency reciprocating rig (HFRR) testing, the MWFs exhibited comparable film thickness and friction coefficients compared to corresponding MWTs with water-in-oil emulsions of naphthenic oils. The oil-in-water MWF fluids also exhibited minimal foam formation, less than 50 mm, in a foam test (described below). [Example]

[0061] In the examples, the following tests were carried out on the samples.

[0062] Lubricity Test HFRR (High Frequency Reciprocating Rig): Reports an average film thickness of 63% and a coefficient of friction of 0.104 according to ASTM D6079. This is performed by measuring the electrical resistance between two mating bodies. No resistance is zero percent film, high resistance is 100%.

[0063] Stability Testing: Each sample is tested for initial stability, centrifugation stability, and long-term stability at 60°C for both concentrate and emulsion. Centrifugation stability is checked after 30 minutes at 3000 rpm and observed for separation.

[0064] Foaming tendency: In the foaming test, 100 mL of emulsion in a 250 mL graduated cylinder was shaken for 1 minute, and then the initial foam height and the foam height after standing for 1 minute were measured.

[0065] Particle size: Particle size was measured using a Beckman Coulter Delsa Nanoparticle Analyzer.

[0066] Iron filings corrosion: Evaluated according to ASTM 4267.

[0067] DCR: Kraton Corporation DCR with the properties shown in Table 1 was used in the examples.

[0068] [Table 1]

[0069] Rosin Oil: For comparative examples, rosin oil was prepared according to experimental procedures known in the art, as shown below. The xx designations, such as "AN-26" and "AN-80," refer to the acid number of the (crude) rosin oil sample. PTSA refers to p-toluenesulfonic acid, and PTSA / S refers to experiments with sulfur-containing PTSA.

[0070] Rosin Oil AN-10 (PTSA / S): Rosin acid was heated to 180°C in a round-bottom flask and then charged with 3.75 wt% sulfur. After the sulfur was charged, the temperature was increased and maintained at 230°C. After 4 hours, the reaction mixture was charged with 2 wt% PTSA and the temperature was increased to 290°C. The reaction mixture was maintained at 290°C for 51 hours until an acid number of 10 mg KOH / g was obtained.

[0071] Rosin Oil AN-80 (PTSA / S): AN80 was prepared in the same manner as AN-10, except that the reaction mixture was held at 290° C. for 1 hour to obtain an acid number of 80 mg KOH / g.

[0072] Rosin Oil AN-80 (hot): No catalyst, e.g., PTSA / S, was used in the experiment. The rosin acid was heated at 40°C / hr to 320°C and the reaction was held at 320°C for 75 hours until 80 mg KOH / g was reached.

[0073] Other rosin oils: The above experiment was repeated except that different reaction times were used for rosin oil samples with different acid numbers, e.g., AN-23 (PTSA / S), AN-26 (PTSA / S), and AN-37 (thermal), and a different catalyst (hydrolin) was used for AN-6. These comparative rosin oils are used in Examples 5A-5E.

[0074] Distillate Examples: Several of the prior art rosin oil and DCR samples were purified to obtain distillate samples. The properties of the crude DCR are shown below in Table 2A, and the properties of the distilled DCR are shown below in Table 2B.

[0075] [Table 2]

[0076] [Table 3]

[0077] Examples 1A-1F Solubilized Oil MWF in DI Water: MWF formulations were prepared from different concentrates having the components listed in Table 3, substituting different base oils for the naphthenic base oil in Table 3. MWF formulations were prepared by dispersing 56 grams of each concentrate in 644 grams of DI (deionized) water for each sample. The differences between the examples are the base oil components and ratios, as shown in Table 4, with some examples having DCR (acid number of approximately 7 mg KOH / g) and mineral oil-based components. Table 4 also shows stability test results, as well as particle size, foam tendency, lubricity, and corrosivity.

[0078] [Table 4]

[0079] [Table 5]

[0080] Examples 2A-2F—Semi-synthetic MWF in DI Water: MWF formulations were prepared from concentrates having the components listed in Table 5, substituting different base oils. MWF formulations were prepared by dispersing 30 grams of concentrate per sample in 345 grams of DI (deionized) water. As with the previous examples, the differences between the examples are the base oil components and ratios, as shown in Table 6, with some examples having DCR (acid number approximately 7 mg KOH / g) and mineral oil-based components. Table 6 also shows stability test results, as well as particle size, foam tendency, lubricity, and corrosivity.

[0081] [Table 6]

[0082] [Table 7]

[0083] Examples 3A-3F Solubilized Oil MWF in Hard Water: Examples 1A-1F with solubilized oil concentrate formulations were repeated except that the concentrate was dispersed in hard water (DI water containing 500 ppm calcium chloride) instead of simply DI. Table 7 shows the test results for stability, particle size, foam tendency, lubricity, and corrosivity.

[0084] [Table 8]

[0085] Examples 4A-4B: MWF formulations were prepared from different concentrates having the ingredients listed in Table 3, substituting different rosin oils for the naphthenic base oil in Table 3. The MWF formulations were prepared by dispersing 56 grams of each concentrate in 644 grams of hard water per sample. Table 8 shows the stability test results, as well as particle size, foam tendency, lubricity, and corrosivity.

[0086] [Table 9]

[0087] Examples 5B-5E: MWF formulations were prepared from different concentrates having the components listed in Table 3, substituting different rosin oils and distillates for the naphthenic base oil in Table 3. MWF formulations were prepared by dispersing 56 grams of each concentrate in 644 grams of hard water per sample. Table 9 shows the results of stability testing, particle size, foam tendency, lubricity, and corrosivity.

[0088] [Table 10]

[0089] Examples 6A-6E: MWF formulations were made from different concentrates having the ingredients listed in Table 3, with 56 grams of each concentrate added to 644 grams of hard water, substituting olive oil, methyl oleate, and isopropyl oleate for the naphthenic base oil in Table 3. Table 10 shows the stability test results, as well as particle size, foam tendency, lubricity, and corrosivity.

[0090] [Table 11]

[0091] Examples 7A-7F Semi-Synthetic MWF in Hard Water: Examples 2A-2F with semi-synthetic concentrate formulations were repeated except that the concentrate was dispersed in hard water (DI water containing 500 ppm calcium chloride) instead of simply DI. Table 11 shows the test results for stability, particle size, foam tendency, lubricity, and corrosivity.

[0092] [Table 12]

[0093] As illustrated, DCR can be substituted for all or part of a mineral oil, e.g., Group I or Group II. A Group II oil that does not produce a stable product when used in the same formulation can be supplemented with 50% DCR to produce a stable product. Replacing 50% of the naphthenic oil with paraffinic oil does not provide the same improvement. While some differences are observed when formulating with hard water instead of DI water, primarily with regard to long-term stability at 60°C, the differences between conventional oils and DCR are minimal.

[0094] Although various embodiments are described herein using the terms "comprising" and "including," the terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to indicate more specific embodiments of the present disclosure, and are also disclosed.

Claims

1. 1. A metalworking fluid concentrate used as an oil-in-water emulsion, comprising: a base oil component in an amount of 5 to 90 wt. %, based on the total weight of the concentrate; an emulsifier selected from any of the typical anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants in an amount of 0.1 to 15% by weight; containing at least one additive selected from a saponifying agent, a pH buffer, a preservative, an extreme pressure EP additive, a corrosion inhibitor, an antiwear agent, a metal deactivator, a defoamer, a rust inhibitor, a deodorizer, a dye, a mildew inhibitor, a bactericide, an antioxidant, an emulsion stabilizer, and a dispersion stabilizer in an amount of 0.1 to 15% by weight; the base oil component comprises at least 50 wt. % decarboxylated rosin acid (DCR), based on the total weight of the base oil component, with the remaining components selected from naphthenic oils, paraffinic oils, bio-based oils, and mixtures thereof; DCR is m / z (mass / charge) measured by GC-FID-MS is 220-280; The oxygen content obtained by elemental analysis is less than 5%; an acid number, measured using ASTM 28-18, of less than 10 mg KOH / g; DCR is greater than 50% by weight of tricyclic and polycyclic compounds having 18 to 20 carbon atoms as determined by GC-FID-MS; More than 55% by weight of tricyclic compounds as aromatic and alicyclic, as determined by GC-FID-MS; and A metalworking fluid concentrate containing less than 45% by weight of tricyclic compounds as reactive double bonds (C=C groups) as determined by GC-FID-MS.

2. 2. The metalworking fluid concentrate of claim 1, wherein the DCR has an aromatics content of greater than 25 wt.%, a naphthene content of greater than 40 wt.%, and a paraffin content of greater than 15 wt.%, all by ASTM D2140 based on the total weight of the DCR.

3. DCR is, Brookfield viscosity by ASTM D-445 greater than 20 cSt at 40°C; an aniline point according to ASTM D611 of at least 5°C; Pour point according to ASTM D97 of less than 30°C; a sulfur content measured in accordance with ASTM D5453 of less than 0.05 wt.%; Gardner color scale according to ASTM D6166 of less than 3, and 10. The metalworking fluid concentrate of claim 1, having at least one flash point according to ASTM D92 of less than 160°C.

4. The metalworking fluid concentrate of claim 1, wherein the amount of tricyclic compounds as alicyclics in the DCR exceeds 30 wt. % as measured by GC-FID-MS.

5. A metalworking fluid concentrate described in any one of claims 1 to 4, wherein the total amount of tricyclic compounds as aromatic and alicyclic compounds in the DCR measured by GC-FID-MS is more than 60 weight % based on the total weight of the DCR.

6. A metalworking fluid concentrate described in any one of claims 1 to 4, wherein the amount of tricyclic compounds as reactive double bonds measured by GC-FID-MS is less than 30 wt% based on the total weight of the DCR.

7. A metalworking fluid concentrate according to claim 1, wherein the amount of reactive double bond DCR, as measured by GC-FID-MS, is less than 10% by weight based on the total weight of DCR.

8. A metalworking fluid concentrate according to any one of claims 1 to 4, wherein the concentrate is a solubilised oil concentrate and the amount of base oil component is from 40 to 90 wt%, based on the total weight of the concentrate.

9. A metalworking fluid concentrate according to any preceding claim, wherein the concentrate is a semi-synthetic fluid concentrate and the amount of base oil component is from 5 to 40 wt%, based on the total weight of the concentrate.

10. A metalworking fluid concentrate according to any one of claims 1 to 4, wherein the base oil component comprises more than 50 wt% DCR, based on the total weight of the base oil component, the remainder being a Group I base oil.

11. 1. A method of preparing a metal surface for subsequent metal processing to produce an article from said metal, comprising: diluting the MWF concentrate according to any one of claims 1 to 4 with water to form a metalworking fluid (MWF) as an oil-in-water emulsion, the concentration of water being 80 to 99% based on the total weight of the MWF; and applying the oil-in-water emulsion as a substantially continuous layer onto a metal surface to deposit an ultra-thin film of the metalworking fluid on the metal surface.

12. 1. A method of preparing a metal surface for subsequent processing of the metal to produce an article of manufacture therefrom, comprising: a base oil component in an amount of 5 to 90 wt. %, based on the total weight of the concentrate; an emulsifier selected from any of the typical anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants in an amount of 0.1 to 15% by weight; containing at least one additive selected from a saponifying agent, a pH buffer, a preservative, an extreme pressure EP additive, a corrosion inhibitor, an antiwear agent, a metal deactivator, a defoamer, a rust inhibitor, a deodorizer, a dye, a mildew inhibitor, a bactericide, an antioxidant, an emulsion stabilizer, and a dispersion stabilizer in an amount of 0.1 to 15% by weight; the base oil component comprises at least 50 wt. % decarboxylated rosin acid (DCR), based on the total weight of the base oil component, with the remaining components selected from naphthenic oils, paraffinic oils, bio-based oils, and mixtures thereof; DCR is m / z (mass / charge) measured by GC-FID-MS is 220-280; The oxygen content obtained by elemental analysis is less than 5%; an acid number, measured using ASTM 28-18, of less than 10 mg KOH / g; DCR is greater than 50% by weight of tricyclic and polycyclic compounds having 18 to 20 carbon atoms as determined by GC-FID-MS; More than 55% by weight of tricyclic compounds as aromatic and alicyclic, as determined by GC-FID-MS; and A method comprising providing a metalworking fluid concentrate containing less than 45 wt. % tricyclic compounds as reactive double bonds (C=C groups) as measured by GC-FID-MS.

13. 13. The process of claim 12, wherein the DCR has an aromatics content of greater than 25 wt%, a naphthene content of greater than 40 wt%, and a paraffin content of greater than 15 wt%, all by ASTM D2140 based on the total weight of the DCR.

14. The method of claim 12 or 13, wherein the amount of tricyclic compounds as alicyclics in the DCR is greater than 30% by weight as measured by GC-FID-MS.

15. DCR is, Brookfield viscosity by ASTM D-445 greater than 20 cSt at 40°C; an aniline point according to ASTM D611 of at least 5°C; Pour point according to ASTM D97 of less than 30°C; a sulfur content measured in accordance with ASTM D5453 of less than 0.05 wt.%; Gardner color scale according to ASTM D6166 of less than 3, and 14. The method of claim 12 or 13, having at least one flash point according to ASTM D92 of less than 160°C.

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