Metal-working fluid composition and production method

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] This disclosure relates to a bio-based metalworking fluid (MWF) composition and a method for producing the same, and more particularly to a metalworking fluid containing decarboxylated rosinic acid as a lubricant, with improved emulsification stability. [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 it, extend tool life (net), and remove metal chips. Examples of such metalworking fluids include oily substances (base oils), such as mineral oil, animal oil, vegetable oil, or synthetic oil, water, and surfactant compounds. Metalworking fluids containing mineral oil present industrial challenges in terms of their origin from petroleum (fossil fuels) and their ability to emulsify to form a stable emulsion. [Overview of the Initiative] [Problems that the invention aims to solve]

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

[0004] In one embodiment, a bio-based metalworking fluid concentrate is provided. The metalworking fluid concentrate comprises 5 to 90% by weight of a base oil component based on the total weight of the concentrate, 0.1 to 15% by weight of an emulsifier selected from typical anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, and 0.1 to 15% by weight of at least one optional additive selected from saponifiers, pH buffers, preservatives, extreme pressure EP additives, corrosion inhibitors, wear inhibitors, metal deactivators, defoamers, rust inhibitors, deodorizers, dyes, antifungal agents, bactericides, antioxidants, emulsifying stabilizers and dispersion stabilizers, wherein the base oil component contains at least 50% by weight of decarboxylated rosinic acid (DCR) oil based on the total weight of the base oil component. DCR oil contains 50-100% by weight of a tricyclic compound having 18-20 carbon atoms, possessing one or more C=C groups, with 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.

[0005] In another embodiment, a method is provided for preparing a metal surface for subsequent metalworking to produce a product. The method comprises diluting an MWF concentrate with water to form a metalworking fluid (MWF) as an oil-in-water emulsion such that the water concentration is 80–99% of the total weight of the MWF, and coating the metal surface with this oil-in-water emulsion as a substantially continuous layer to deposit an ultrathin film of the metalworking fluid onto the metal surface. The DCR oil comprises 50–100% by weight of a tricyclic compound having 18–20 carbon atoms, having one or more C=C groups, and having an m / z (mass / charge) value of 220–280. The DCR contains more than 50% by weight of tricyclic and polycyclic compounds with 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 of the total weight of the DCR, and the sum of the amounts of tricyclic compounds as aromatic DCRs and alicyclic DCRs in the DCR exceeds 55% of the total weight of the DCR. [Modes for carrying out the invention]

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

[0007] "At least one of the groups [A, B, and C, etc.]", "any of the groups [A, B, and C, etc.]", or "selected from [A, B, and C] and their combinations" means a single element of a group, one or more elements of a group, or a combination of elements of a 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] The list of embodiments presented as "A, B, or C" should be interpreted as including 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 desalinated water (DM water) is water from which almost all inorganic ions, such as cations like sodium, calcium, iron, and copper, and anions like chlorides and sulfides, have been removed.

[0010] "Metalworking fluid" can be used interchangeably with MWF, or "metalworking composition," "metal removal fluid," "cutting fluid," or "processing fluid," and refers to a composition usable in industrial metal cutting or metal grinding processes, or in the semiconductor industry, where the final product, such as a silicon wafer or machine part, is obtained by, or without, stepwise removal of metal or silicon. Among its functions, metalworking fluid is used particularly for cooling and lubrication.

[0011] "Solubilized oil" refers to MWF (Water-Based Fluid) supplied to end users as an oil-in-water solution containing a substantial amount of water and special additives. The oil content in the solubilized oil MWF concentrate ranges from 40 to 90%, and the oil content in the final MWF applied ranges from approximately 5 to 10% by weight, which is typically diluted with water at the user's site.

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

[0013] Weight percentage refers to weight concentration.

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

[0015] This disclosure relates to a bio-based metalworking fluid ("MWF") composition and a method for producing the same, and more particularly to an MWF comprising a bio-based base oil with improved emulsification stability. The bio-based base oil is a plant-derived decarboxylated rosinic acid ("DCR") liquid product.

[0016] Water component: The metalworking fluid contains a water layer which may be deionized water (DI water), 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 site of use) is 80-99%, 85-92%, or more than 90%, or 95% or less, or 99% or less, of the total weight of the final MWF.

[0018] Main component - Decarboxylated rosinic acid (DCR) as base oil: In some embodiments, MWF contains DCR as the sole base oil component (100%), or in excess of 50% by weight, 60% by weight, or 70% by weight of the base oil component. DCR may be crude DCR, distilled DCR, refined DCR (purity exceeding 90%), or a mixture thereof. Crude DCR has a composition similar to distilled DCR from which heavy fractions (10-15%) have been removed for color improvement and sulfur reduction, etc.

[0019] DCR is produced by decomposing rosinic acid at high temperatures. Rosinic acid is typically a solid with a softening point of, for example, 65-85°C. Rosinic acid is not petroleum-derived, but rather plant-derived from (pine) resin, (tree) stump, and tall oil (a papermaking by-product). Rosinic acid can be completely or partially decarboxylated to form decarboxylated rosinic acid (DCR or DCR oil).

[0020] DCR is, for example, C 20 H 30 DCR is a mixture of molecules containing monocarboxylic acids having the general molecular formula O2. In some embodiments, DCR is characterized by containing 40–100% by weight of tricyclic and polycyclic compounds having 18–20 carbon atoms, one or more C=C groups, and having m / z (mass / charge) values ​​measured by GC-FID-MS of 220–280, 230–270, 234–262, 235–265, or in the range of greater than 230 or less than 265. m / z is defined as the molecular weight (MW) of the compound divided by the charge, which is approximately 1 in the case of DCR.

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

[0022] In some embodiments, the amount of alicyclic DCR exceeds 30 wt%, or exceeds 40 wt%, or exceeds 50 wt%, or exceeds 80 wt% based on the total weight of 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 DCR. The reactive C=C groups are defined as DCR species with MW of 254 and 258.

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

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

[0026] ​DCR has a lower acid value (carboxylic acid content) than rosin acid. In some embodiments, DCR has an acid value 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 2 to 30 mg KOH / g, or 4 to 25 mg KOH / g, or 5 to 20 mg KOH / g.

[0027] In some embodiments, the DCR has an aromatic content of 30–60% by weight, 32–56% by weight, 35–54% by weight, 38–52% by weight, or 40–50% by weight relative to the total weight of the DCR, or greater than 30% by weight or less than 45% by weight.

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

[0029] In some embodiments, the DCR has a paraffinic content of 20–35% by weight, 22–34% by weight, 24–32% by weight, or 26–30% by weight relative to the total weight of the DCR, or greater than 22% by weight or less than 32% by weight.

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

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

[0032] In some embodiments, the DCR has a pour point of -30 to +10°C, -28 to +8°C, or -25 to +5°C according to ASTM D97, 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 is a boiling point measured according to D2887 that is between 235 and 390°C, or greater than 230°C, or less than 400°C.

[0035] In some embodiments, the DCR is a Gardner color number 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 according to ASTM D6166, 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 that is less than 0.05% by weight, or less than 0.04% by weight, or less than 0.03% by weight, less than 0.02% by weight, or less than 0.01% by weight, or less than 0.001% by weight, or between 40 and 200 ppm, or less than 500 ppm, or less than 100 ppm.

[0037] In some embodiments, the DCR is defined as having a VOC content of less than 5% by weight, or less than 4.75% by weight, or less than 4.5% by weight, or less than 4.25% by weight, or less than 4.0% by weight, or less than 3.75% by weight, or less than 3.5% by weight, or less than 3.25% by weight, or less than 3.0% by weight, or less than 2.75% by weight, or less than 2.5% by weight, or less than 2.25% by weight, or less than 2.0% by weight, or less than 1.5% by weight, or less than 1.0% by weight, or less than 0.5% by weight. The VOCs in the DCR are measured by summing the weight percentage contributions of all VOCs present in the product at a concentration of 0.01% or more, in accordance with EPA Act 24 or an equivalent method.

[0038] In some embodiments of the semi-synthetic liquid MWF, the amount of DCR oil is 5 to 40% by weight of the total weight of the MWF concentrate, or is in the range of more than 5% by weight, more than 30% by weight, more than 35% by weight, or less than 45% by weight.

[0039] In some embodiments of the solubilized oil MWF, the amount of DCR is in the range of 40 to 90% by weight of the total weight of the MWF concentrate, or greater than 55% by weight, greater than 60% by weight, greater than 65% by weight, or less than 85% by weight.

[0040] Optional base oil component: In some embodiments, in addition to DCR, small amounts of (different) oils can be used 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 crude oil, intermediate crude oil or naphthenic crude oil, vegetable oil (e.g., soybean oil), short branched chain esters derived from fats and oils (e.g., methyl esters for soybeans, isopropyl oleate and trimethylolpropane oleate), and refined oils obtained by refining these distillates.

[0042] If additional base oils (other than DCR) are used, their amount is less than 50% of the total base oil amount. In some embodiments of the semi-synthetic liquid, the amount of additional base oil used is in the range of 2-25%, less than 20%, or less than 10% of the total weight of the MWF. In some embodiments of the solubilized oil, if additional base oils are used, their amount is in the range of 20-45% by weight, less than 40%, less than 30%, or less than 20% of the total weight of the MWF concentrate.

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

[0044] Emulsifier component: MWF further comprises at least one emulsifier, preferably two or more emulsifiers (e.g., an emulsifier and an auxiliary emulsifier) ​​which may be homogeneous or heterogeneous. The choice of emulsifier depends on the amount of water, as well as the amount and type of oil component used. The emulsifier is selected from among typical anionic surfactants, cationic surfactants, nonionic surfactants, or amphoteric surfactants.

[0045] In some embodiments, the emulsifier component is selected from amphoteric compounds. Examples include alkyl-3-iminodipropionates, alkyl-3-aminopropionates, fatty imidazolines and betaines, more specifically 1-coco-5-hydroxyethyl-5-carboxymethylimidazoline, dodecyl-3-alanine, N-dodecyl-N,N-dimethylaminoacetic acid, and intramolecular salts of 2-trimethylaminolauric acid.

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

[0047] In some embodiments, the emulsifier composition is selected from cationic compounds including cetylpyridium bromide, hexadecylmorpholinium chloride, dilauryltriethylenetetramine diacetate, didodecylamine lactate, 1-amino-2-heptadecenylimidazoline acetate, cetylamine acetate, oleylamine acetate, and ethoxylated animal fats, coconut, stearyl, oleyl, or soy amines. Useful anionic compounds include alkali metal salts of petroleum sulfonic acid, alkali metal salts of fatty acids, fatty acid amines and ammonium soaps, alkali metal dialkyl sulfosuccinates, sulfated oils, sulfonated oils, and alkali metal alkyl sulfates.

[0048] In some embodiments, the emulsifier is an oil-soluble emulsifier such as an organic sulfonate, a fatty acid ester, polyoxyethylene acid, alcohol, and alkanolamide, and alkanolamine, with the latter generally 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 the main emulsifier or as an auxiliary emulsifier in combination with other emulsifiers (e.g., sulfonates).

[0050] The amount of emulsifier is in the range of 0.1–15%, 0.3–12%, or at least 10% of the total weight of the MWF concentrate.

[0051] Optional components: The metalworking fluid optionally contains one or more components selected from saponifying agents or (pH) buffering agents, preservatives, extreme pressure (EP) additives or anti-wear additives, corrosion inhibitors, anti-wear agents, metal deactivators, defoaming agents, rust inhibitors, deodorizers, dyes, antifungal agents, fungicides, antioxidants, emulsifying stabilizers or dispersion stabilizers, etc.

[0052] Examples of saponifying agents / buffers 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 oxides, organic diamines, organic amine condensates of fatty alcohols, and substituted imidazolines.

[0054] Examples of wear inhibitors (AW, lubrication improvers) include organic acids. Examples of such organic acids include 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 dodecanedionic acid.

[0055] In some embodiments, MWF comprises at least one extreme pressure (EP) / coupling agent selected from typical coupling agents such as zinc dithiophosphate (ZDP), zinc dialkyldithiophosphate (ZDDP), triglyceryl phosphate (TCP), halocarbons (chlorinated paraffin), 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 to 15% by weight, or less than 10% by weight, or greater than 0.5% by weight, or less than 5% by weight, or less than 2% by weight, depending on the optional additive.

[0057] Preparation Method / Application: Depending on the base oil used (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 a 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] For use, the concentrate is then dispersed in water using a high-shear mixer, such as those used in metalworking processes like cutting, crushing, punching, polishing, deep drawing, drawing, and rolling, thereby producing MWF that provides excellent lubrication for processing so-called difficult-to-process materials.

[0059] Characteristics: Metalworking fluids prepared from concentrates using DCR (or a mixture of DCR and a different base oil) as the base oil component are characterized as exhibiting equivalent or better performance compared to MWF prepared solely from mineral oils, such as Group I or Group II oils.

[0060] In embodiments using base oil components containing at least 50% DCR (based on the amount of DCR in the total amount of base oil components), the prepared MWF exhibits excellent stability even after 28 days at 60°C. In high-frequency reciprocating rig (HFRR) tests, the MWF showed comparable film thickness and coefficient of friction to the corresponding MWT made of a naphthenic oil water-in-oil emulsion. The oil-in-water MWF liquid also exhibited minimal foam formation of less than 50 mm in the foaming test (described below). [Examples]

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

[0062] Lubricity test HFRR (High Frequency Reciprocating Rig): According to ASTM D6079, an average film thickness of 63% and a friction coefficient of 0.104 are reported. This is performed by measuring the electrical resistance between two joined objects. Zero percent film thickness corresponds to no resistance, and 100% corresponds to high resistance.

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

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

[0065] Particle size: Particle size was measured using a Beckman Coulter DELSA nanoparticle analyzer.

[0066] Scrap corrosion was evaluated according to ASTM 4267.

[0067] DCR: The DCR of Clayton Corporation, which has the characteristics shown in Table 1, was used as an example.

[0068] [Table 1]

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

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

[0071] Rosin oil AN-80 (PTSA / S): AN80 was obtained in the same manner as AN-10, except that the reaction mixture was kept at 290°C for 1 hour so that the acid value was 80 mg KOH / g.

[0072] Rosin oil AN-80 (thermal): No catalyst, such as PTSA / S, was used in the experiment. Rosin acid was heated at 40°C / hour up to 320°C, and the reaction was held at 320°C for 75 hours until it reached 80 mg KOH / g.

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

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

[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, by substituting the naphthenic base oils in Table 3 with different base oils. For each sample, 56 grams of each concentrate was dispersed in 644 grams of DI (deionized) water to prepare the MWF formulation. The differences between the examples are the base oil components and ratios, as shown in Table 4, and some examples have DCR (with an acid value of approximately 7 mg KOH / g) and mineral oil components. Table 4 also shows particle size, foaming tendency, lubricity, and corrosiveness, along with the stability test results.

[0078] [Table 4]

[0079] [Table 5]

[0080] Examples 2A-2F - Semi-synthetic MWF in DI water: MWF formulations were produced from concentrates having the components listed in Table 5, with the base oil being replaced by different base oils. For each sample, 30 grams of concentrate was dispersed in 345 grams of DI (deionized) water to produce the MWF formulation. Similar to the above examples, the differences between the examples are the base oil components and ratios, as shown in Table 6, and some examples contain DCR (with an acid value of approximately 7 mg KOH / g) and mineral oil components. Table 6 also shows particle size, foaming tendency, lubricity, and corrosiveness, along with the stability test results.

[0081] [Table 6]

[0082] [Table 7]

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

[0084] [Table 8]

[0085] Examples 4A-4B: MWF formulations were prepared from different concentrates having the components listed in Table 3, by substituting the naphthenic base oils in Table 3 with different rosin oils. For each sample, 56 grams of each concentrate was dispersed in 644 grams of hard water to prepare the MWF formulation. Table 8 shows the particle size, foaming tendency, lubricity, and corrosiveness, along with the stability test results.

[0086] [Table 9]

[0087] Examples 5B-5E: MWF formulations were prepared from different concentrates having the components listed in Table 3, by substituting the naphthenic base oils in Table 3 with different rosin oils and distillates. For each sample, 56 grams of each concentrate was dispersed in 644 grams of hard water to prepare the MWF formulation. Table 9 shows the stability test results, particle size, foaming tendency, lubricity, and corrosiveness.

[0088] [Table 10]

[0089] Examples 6A-6E: MWF formulations were prepared by adding 56 grams of each concentrate to 644 grams of hard water, replacing the naphthenic base oil in Table 3 with olive oil, methyl oleate, and isopropyl oleate. Table 10 shows the particle size, foaming tendency, lubricity, and corrosiveness, along with the stability test results.

[0090] [Table 11]

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

[0092] [Table 12]

[0093] As illustrated, DCR can be substituted for all or part of mineral oil, such as Group I or Group II oils. A stable product can be produced by supplementing Group II oils that do not produce a stable product when used in the same formulation with 50% DCR. Replacing 50% of naphthenic oil with paraffin oil does not yield the same improvement. While some differences are observed when hard water is used instead of DI water in the formulation, the difference between conventional oils and DCR is extremely small, mainly in terms of long-term stability at 60°C.

[0094] While the terms “comprising” and “including” have been used to describe various aspects in this specification, the terms “consisting essentially of” and “consisting of” may be used instead of “comprising” and “including,” and these are also disclosed.

Claims

1. 1. A metalworking fluid concentrate for use 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, cationic, nonionic and zwitterionic surfactants in an amount of 0.1 to 15% by weight; 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 fungicide, 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, the remaining components being 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, as measured using ASTM 28-18, of less than 10 mg KOH / g; DCR is, More 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 of 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, as determined according to ASTM D5453, of less than 0.05% by weight; 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% by weight as measured by GC-FID-MS.

5. A metalworking fluid concentrate described in any one of claims 1 to 4, wherein the sum of the amount of tricyclic compounds as aromatics and alicyclics 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 weight % 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 one of claims 1 to 4, 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 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 80-99% based on the total weight of the MWF; 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 the steps of: 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, cationic, nonionic and zwitterionic surfactants in an amount of 0.1 to 15% by weight; 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 fungicide, 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, the remaining components being 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, as measured using ASTM 28-18, of less than 10 mg KOH / g; DCR is, More 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 alicyclic compounds in the DCR is greater than 30% by weight as measured by GC-FID-MS.

15. DCR is, Brookfield viscosity by ASTM D-445 of 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, as determined according to ASTM D5453, of less than 0.05% by weight; 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.