JP2010535276A - Isomerized base oil metalworking fluid compositions with improved defoaming properties and their preparation - Google Patents

Abstract

  A metalworking fluid is provided comprising an isomerized base oil having a sequential number of carbon atoms and less than 10% by weight naphthenic carbon by ndM. The metalworking fluid exhibits reduced mist formation, low foaming, and excellent defoaming properties.

Description

  The present invention generally relates to metalworking compositions that exhibit improved anti-misting properties with low foaming and excellent defoaming properties.

  Industrial metal cutting operations, such as cutting silicon wafers by the semiconductor industry, use machining fluids or metal working fluids to assist or enhance the cutting process. The metal working fluid can be used as cutting oil, rolling oil, drawing oil, pressure forming oil, forging oil, aluminum disk polishing oil, silicon wafer polishing oil and coolant. In high speed machining operations involving high speed fluid application and recirculation, entrapment of bubbles and air can have undesirable consequences. Foaming is undesirable because it can reduce cooling at the workpiece-tool or swarf-tool interface and cause uptake transport and control problems. Various methods or strategies have been taken to eliminate or reduce foaming, including the addition of foam inhibitor (s) during product manufacture or during use of the fluid. The use of certain foam inhibitor (s), such as silicone antifoam agents, can leave residue on the machined part and make subsequent painting of that part difficult. Furthermore, some foam suppressor (s) may worsen the defoaming properties of the metalworking fluid.

  The defoaming property of a fluid can also be critical for its use performance, especially for high speed operations. In some cases, the use of poorly defoamed fluids can lead to air intake problems and cavitation of machine parts.

  In addition to foaming and defoaming, another common in-use problem associated with metalworking fluids is the generation of fog or mist. During the cutting process, a small amount of cutting oil tends to escape into the surrounding air as micro-sized droplets known as mist. A nearby worker is exposed to the mist, and some mist can be aspirated into the operator's lungs unless the protective breathing apparatus is worn. Prior art metal cutting fluids are essential for machining, but they are currently under scrutiny because of the dangers that can occur with worker exposure.

  Various additives are used to reduce mist formation, including the use of small amounts of at least one polyisobutene, poly-n-butene and mixtures thereof having a viscosity average molecular weight in the range of 300,000 to 10 million. Attempts have been made in the prior art. Rhamsan gum, hydrophobic and hydrophilic monomers, styrene or hydrocarbyl-substituted styrene hydrophobic monomers and hydrophilic monomers have been suggested for use to reduce mist formation among additives. Some prior art metal cutting fluids related to the use of various additives cause environmental problems with their disposal. There is now unanimous agreement on the need for safer and more environmentally friendly metalworking fluids.

  Recent reforming processes have produced a new class of oils, such as Fischer-Tropsch base oil (FTBO), where the oil, fraction, or feed is part of the Fischer-Tropsch process. Or produced there. The feedstock for the Fischer-Tropsch process can be provided by a wide variety of hydrocarbon-based resources including biomass, natural gas, coal, shale oil, petroleum, municipal waste, derivatives thereof, and combinations thereof. The crude product prepared from the Fischer-Tropsch process can be refined into products such as diesel oil, naphtha, wax, and other liquid petroleum or specialty products. Many patent publications and applications, ie, US Patent Publication No. 2006/0289337, US Publication No. 2006/0201851, US Publication No. 2006/0016721, US Publication No. 2006, which are incorporated herein by reference. US Patent Publication No. 2006/0076267, US Patent Publication No. 2006/020185, US Patent Publication No. 2006/013210, US Patent Publication No. 2005/0241990, US Patent Publication No. 2005/0077208, US Patent Publication No. 2005/0139513, United States Patent Publication No. 2005/0139514, United States Patent Publication No. 2005/0133409, United States Patent Publication No. 2005/0133407, United States Patent Publication No. 2005/02611147, United States Patent Publication No. 20 No. 5/02611146, U.S. Patent Publication No. 2005/0261145, U.S. Patent Publication No. 2004/0159582, U.S. Patent No. 7018525, U.S. Patent No. 7083713, U.S. Patent Application No. 11/400570, and No. 11/535165. No. 11/613936, the isomerized base oil is produced from a process in which the feedstock is a waxy feedstock recovered from Fischer-Tropsch synthesis. This process involves a complete or partial hydroisomerization dewaxing step using a dual function catalyst or a catalyst capable of selectively isomerizing paraffins. Hydroisomerization dewaxing is obtained by contacting the waxy feed with a hydroisomerization catalyst in the isomerization zone under hydroisomerization conditions.

  There is a need for improved metalworking fluids that have reduced mist and foam formation and superior defoaming properties as compared to prior art compositions.

  In one embodiment, a lubricating base oil having a sequential number of carbon atoms and less than 10 wt% naphthenic carbon by ndM; and a metalworking fluid additive package; a metal deactivator; a corrosion inhibitor; Antibacterial agent; anticorrosive agent; extreme pressure agent; antifriction agent; rust inhibitor; polymeric substance; anti-inflammatory agent; antibacterial agent; antiseptic agent; antioxidant agent; chelating agent such as edetate salt; There is provided a metalworking fluid comprising 0.10 to 10% by weight of at least one additive selected from the group consisting of a wear agent and mixtures thereof, wherein the metalworking fluid is ASTM D3427- It has a defoaming property of less than 0.6 minutes at 50 ° C. according to 03 and a Sequence II foaming rate of less than 50 mL according to ASTM D892-03.

  In another aspect, a method for improving foaming and defoaming properties of a metalworking fluid comprising a base number of carbon atoms and less than 10 wt% naphthenic carbon by ndM A metal processing fluid additive package; a metal deactivator; a corrosion inhibitor; an antibacterial agent; an anticorrosive agent; an extreme pressure agent; an anti-friction agent; a rust inhibitor; Preservatives; antioxidants; chelating agents such as edetates; pH adjusters; antiwear agents and at least one of 0.10 to 10% by weight selected from the group consisting of mixtures thereof A method is provided that includes blending the additives.

It is a graph which illustrates the mist accumulation rate of Example 7-13 in an aerosol mist formation test. It is a graph which illustrates the mist accumulation rate of Example 7-13 in an aerosol mist formation test. It is a graph which illustrates the mist accumulation rate of Example 7-13 in an aerosol mist formation test.

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

  As used herein, the term “metal working fluid” refers to the final object shape, eg, a silicon wafer or mechanical part, with or without gradual removal of metal or silicon, Synonymous with “metalworking composition”, “metal removal fluid”, “cutting fluid”, “machining fluid”, which refers to a composition that can be used in industrial metal cutting, metal grinding operations or in the semiconductor industry. Can be used. Among other functions, metalworking fluids are used for cooling and lubrication.

  “Fischer-Tropsch derived” means that the product, fraction, or raw material originates from or is produced at some stage by the Fischer-Tropsch process. As used herein, “Fischer-Tropsch base oil” means “FT base oil”, “FTBO”, “GTL base oil” (GTL: gas-to-liquid), or “Fischer-Tropsch derived group”. It can be used synonymously with “oil”.

  As used herein, “isomerized base oil” refers to a base oil produced by isomerization of a waxy feedstock.

  As used herein, “waxy raw material” comprises at least 40% by weight of n-paraffin. In one embodiment, the waxy feed comprises greater than 50% by weight n-paraffins. In another embodiment, greater than 75% by weight n-paraffins. In one embodiment, the waxy feed has very low levels of nitrogen and sulfur, such as less than 25 ppm total nitrogen and sulfur, or in other embodiments less than 20 ppm. Examples of waxy raw materials include slack wax, deoiled slack wax, refined foot oil, waxy lubricating raffinate, n-paraffin wax, NAO wax, wax produced by chemical factory process, deoiled petroleum derived wax, microcrystals Waxes, Fischer-Tropsch waxes, and mixtures thereof are included. In one embodiment, the waxy feed has a pour point of greater than 50 ° C. In another embodiment, it has a pour point above 60 ° C.

“Kinematic viscosity” is a measurement in mm ² / s of resistance to fluid flow under gravity as determined by ASTM D445-06.

  “Viscosity Index” (VI) is an empirical, unitless number showing the effect of temperature changes on the kinematic viscosity of the oil. The higher the VI of the oil, the lower its tendency to change viscosity with temperature. The viscosity index is measured according to ASTM D2270-04.

  The cold crack simulator apparent viscosity (CCS VIS) is a measured value in millipascal second, mPs, for measuring the viscosity characteristics of a lubricating base oil under low temperature and high shear. CCS VIS is determined by ASTM D5293-04.

  Boiling range distribution of base oil by weight% is ASTM D 6352-04, “Boiling Range Distribution of Petroleum Distillation in Boiling Range from 174 by Gas Chromatography. to 700 ° C. by Gas Chromatography) ”by simulated distillation (SIMDIS).

  “Noack volatility” is measured in accordance with ASTM D5800-05, Procedure B, lost in weight percent when the oil is heated at 250 ° C. with a steady flow of air drawn through the oil for 60 minutes. Defined as the mass of oil.

  The Brookfield viscosity is used to determine the internal fluid-friction of the lubricant during cold work, which can be measured with ASTM D2983-04.

  “Pour point” is a measurement of the temperature at which a sample of base oil begins to flow under certain carefully controlled conditions, which can be determined as described in ASTM D5950-02.

  “Auto-ignition temperature” is the temperature at which a fluid ignites spontaneously in contact with air and can be determined according to ASTM 659-78.

  “Ln” refers to the natural logarithm with base “e”.

  “Traction coefficient” is an index of an inherent lubricant property, expressed as a dimensionless ratio of frictional force F and normal force N, where friction resists movement between sliding surfaces or rotating surfaces. Or it is the mechanical force that prevents it. The traction coefficient is PCS Instruments, composed of 19 mm diameter balls (SAE AISI 52100 steel) polished at an angle of 220 to a flat 46 mm diameter polished disk (SAE AISI 52100 steel). It can be measured by the MTM traction measurement system made by Ltd. The steel balls and disks are independently measured at an average rotational speed of 3 meters per second, a slide to 40% rotation ratio, and a 20 Newton load. The rotation ratio is defined as the difference in sliding speed between the ball and disk divided by the average speed of the ball and disk, ie rotation ratio = (speed 1−speed 2) / ((speed 1 + speed 2) − / 2). The

  As used herein, “sequential number of carbon atoms” means that the base oil has a distribution of hydrocarbon molecules over a range of carbon numbers, with all the numbers of intermediate carbon numbers. For example, the base oil may have hydrocarbon molecules that range from C22 to C36 or C30 to C60, with all intermediate carbon numbers. As a result of the waxy raw material also having consecutive numbers of carbon atoms, the hydrocarbon molecules of the base oil differ from one another by consecutive numbers of carbon atoms. For example, in a Fischer-Tropsch hydrocarbon synthesis reaction, the carbon atom source is CO, and the hydrocarbon molecules are formed one carbon atom at a time. Petroleum-derived waxy raw materials have consecutive numbers of carbon atoms. In contrast to oils based on poly-alpha-olefins (“PAO”), isomerized base oil molecules have a relatively long skeleton with more linear structures and short branches. The PAO classic textbook description is a star-shaped molecule, specifically tridecane, which is shown as three decane molecules attached at a central point. Although star molecules are theoretical, nevertheless, PAO molecules have fewer and longer branches than the hydrocarbon molecules that make up the isomerized base oils disclosed herein.

  “Molecule with cycloparaffinic functionality” means any molecule that is a monocyclic or fused polycyclic saturated hydrocarbon group or that contains them as one or more substituents.

  “Molecular with monocycloparaffinic functionality” is any molecule that is a monocyclic saturated hydrocarbon group of 3 to 7 ring carbons, or a single monocyclic saturated carbonization of 3 to 7 ring carbons It means any molecule substituted with a hydrogen group.

  “Molecular with multicycloparaffinic functionality” is any molecule that is a fused polycyclic saturated hydrocarbon ring group of two or more fused rings, one or more fused polycyclic saturated groups of two or more fused rings It means any molecule substituted with a hydrocarbon ring group, or any molecule substituted with two or more monocyclic saturated hydrocarbon groups of 3 to 7 ring carbons.

  Molecules with cycloparaffinic functionality, molecules with monocycloparaffinic functionality, and molecules with multicycloparaffinic functionality are reported as weight percent and are more fully described herein. (FIMS), HPLC-UV for aromatics, and proton NMR for olefins.

Oxidator BN measures the response of the lubricant in a simulated use. High values, ie a long time to absorb 1 liter of oxygen, show good stability. Oxidator BN is a Bordeaux type oxygen absorber (RW Wornte “Oxidation of white oil”), Industrial and Engineering Chemistry, Vol. 28, at 340 ° F. and 1 atmosphere of pure oxygen. 26, 1936) and the time taken to absorb 1000 mL of O ₂ by 100 g of oil is reported. In the Oxidator BN test, 0.8 mL of catalyst is used per 100 grams of oil. The catalyst is a soluble metal-naphthenate mixture that simulates the average metal analysis of the crankcase oil used. The additive package is 80 mmol zinc bispolypropylenephenyl dithiophosphate per 100 g oil.

  Molecular characterization can be performed by methods known in the art, including field ionization mass spectrometry (FIMS) and ndM analysis (ASTM D3238-95) (2005 reapproved). . In FIMS, base oils are characterized as alkanes and molecules with different numbers of unsaturation. Molecules with different numbers of unsaturations can include cycloparaffins, olefins, and aromatics. If aromatics are present in significant amounts, they are identified as 4-unsaturated. If olefins are present in significant amounts, they are identified as 1-unsaturated. Subtract olefin weight% by proton NMR from the sum of 1-unsaturated, 2-unsaturated, 3-unsaturated, 4-unsaturated, 5-unsaturated, and 6-unsaturated from FIMS analysis, and HPLC-UV Minus the weight percent aromatics is the total weight percent of molecules with cycloparaffinic functionality. If the aromatic content is not measured, it is considered to be less than 0.1% by weight and is not included in the calculation of the total weight percent of molecules with cycloparaffinic functionality. The total weight percent of molecules with cycloparaffinic functionality is the sum of the molecular weight percent with monocycloparaffinic functionality and the molecular weight percent with multicycloparaffinic functionality.

  Molecular weight is determined by ASTM D2503-92 (2002 reapproval). This method uses a thermoelectric measurement of vapor pressure (VPO). In situations where sample volume is insufficient, an alternative method of ASTM D2502-04 can be used; if this is used, it is indicated.

  Density is determined by ASTM D4052-96 (2002 reapproved). The sample is introduced into a vibrating sample tube and the change in vibration frequency caused by the change in mass of the tube is used in conjunction with calibration data to determine the density of the sample.

  The olefin weight percent can be determined by proton-NMR according to the steps specified herein. In most tests, the olefin is a conventional olefin, ie, a dispersion mixture of conventional olefin types with hydrogen bonded to a double bond carbon, such as alpha, vinylidene, cis, trans, and tri-substituted. An allyl to olefin detectable integration ratio of .5. If this ratio is greater than 3, it indicates that a relatively high percentage of tri- or tetra-substituted olefin is present, and therefore other assumptions known in the analytical arts make two assumptions in the sample. The number of double bonds can be calculated. The steps are as follows: A) Prepare a solution of 5-10% test hydrocarbon in deuterochloroform, B) Obtain a normal proton spectrum with a spectral width of at least 12 ppm, and a chemical shift (ppm) axis The device has a sufficient gain range to obtain a signal without overloading the receiver / ADC, eg, when applying a 30 degree pulse, the device has a minimum of 65,000. Has a signal digitization dynamic range. In one embodiment, the device has a dynamic range of at least 260,000. C) Measure the integrated intensity between: 6.0-4.5 ppm (olefin); 2.2-1.9 ppm (allyl); and 1.9-0.5 ppm (saturated). D) Using the molecular weight of the test substance determined by ASTM D2503-92 (2002, reapproved), calculate: 1. Average molecular formula of saturated hydrocarbons; 2. Average molecular formula of olefin; 3. total integrated intensity (= sum of all integrated intensities); 4. Integral intensity per sample hydrogen (total integral / number of hydrogens in the formula); 5. Number of olefinic hydrogens (= olefin integral / integral per hydrogen); 6. Number of double bonds (olefin hydrogen × hydrogen in olefin formula / 2); % By weight of olefin by proton NMR = 100 × number of double bonds × number of hydrogen in typical olefin molecule ÷ number of hydrogen in typical test substance molecule. In this test, the olefin weight% according to the proton NMR calculation procedure, D, works particularly well when the olefin percentage result is low, less than 15 weight%.

  The aromatic weight percent in one embodiment can be measured by HPLC-UV. In one embodiment, this test is performed using a Hewlett Packard 1050 Series Gradient High Performance Liquid Chromatography HPLC system coupled with an HP 1050 Diode-Array UV-Vis detector connected to an HP CHem-station. Identification of individual aromatic classes in highly saturated base oils can be based on UV spectral patterns and elution times. The amino column used for this analysis identifies aromatic molecules primarily based on their ring number (or double bond number). Thus, monocyclic aromatic-containing molecules elute first, followed by polycyclic aromatics in order of increasing number of double bonds per molecule. For aromatic compounds with similar double bond properties, those with only alkyl substitution on the ring elute faster than those with naphthene substitution. The unambiguous identification of various base oil aromatic hydrocarbons from the UV absorption spectrum shows that their peak electronic transitions are relative to the pure model compound analogs to a degree that depends on the amount of alkyl and naphthene substitution on the ring system It can be achieved by understanding that all are red-shifted. Quantification of the eluted aromatic compound can be performed by integrating chromatograms generated from wavelengths optimized for each general class of compound over the appropriate retention time frame for that aromatic compound. Retention time frame limits for each class of aromatic compound are determined by manually assessing the individual absorption spectra of the compounds eluting at different times and determining them based on their quantitative similarity to the model compound absorption spectra. It can be determined by assigning to a class of aromatic compounds.

  HPLC-UV assay. In one embodiment, HPLC-UV can be used to identify classes of aromatic compounds even at very low levels, for example, polycyclic aromatic compounds are typically more than monocyclic aromatic compounds. Absorbs about 10 to 200 times stronger. Alkyl substitution affects absorption by 20%. The integration limit for simultaneously eluting 1-ring and 2-ring aromatic compounds at 272 nm can be performed by the vertical drop method. The wavelength depending on the response factor for each general aromatic compound class is first determined by plotting a Beer's law plot from a mixture of pure model compounds based on the closest spectral absorption for the substituted aromatic analog. be able to. The weight percent concentration of aromatics can be calculated by assuming that the average molecular weight for each class of aromatic compound is approximately equal to the average molecular weight for the entire base oil sample.

  NMR analysis. In one embodiment, the weight percent of all molecules having at least one aromatic functional group in the purified monoaromatic standard can be confirmed by long-term carbon-13 NMR analysis. NMR results show that from aromatic carbon% to aromatic molecule% (HPLC-UV and D2007), knowing that 95-99% of aromatic compounds in highly saturated base oils are monocyclic aromatic compounds. Should be consistent). In another test that accurately measures the low level of all molecules with at least one aromatic functional group by NMR, the standard D5292-99 (2004, reapproved) method was modified to provide a 10-12 mm Norarac probe. A minimum carbon sensitivity of 500: 1 (according to ASTM standard practice E386) can be obtained by continuous operation for 15 hours on 400-500 MHz NMR using. Acron PC integration software can be used to define the baseline shape and integrate continuously.

The degree of branching refers to the number of alkyl branches in the hydrocarbon. Branches and branch positions can be determined using carbon-13 ( ¹³ C) NMR according to the following 9-step process: 1) Confirm CH branch center and CH ₃ branch termination point using DEPT pulse sequence (Doddellell, DT; DT Pegg; MR Bendall, Journal of Magnetic Resonance 1982, 48, 323 et seq.) 2) Carbon that initiates multiple branches using APT pulse sequence Confirm the absence of (quaternary carbon) (Patt, S.L .; JN Schoolery, Journal of Magnetic Resonance 1982, 46, 535 onwards), 3) known in the art Using tabulated and calculated values, for a specific branch location and length Assigning branched carbon resonances (Lindman, LP, Journal of Qualitative Analytical Chemistry 43, 1971, 1245 et seq; Netzel, DA, et al., Fuel, 60, 1981, pp 307), 4) Estimate the relative branch density at different carbon positions by comparing the integrated intensity of a specific carbon of a methyl / alkyl group against the intensity of a single carbon (this is the total integral / number of carbons per molecule in the mixture). equal). For 2-methyl branches where both terminal and branched methyl appear at the same resonance position, the intensity is divided by 2 before estimating the branch density. When a 4-methyl branched fragment is calculated and tabulated, its contribution to 4 + methyl is drawn to avoid double calculations 5) Calculate the average carbon number. The average carbon number is determined by dividing the molecular weight of the sample by 14 (CH ₂ formula weight). 6) The number of branches per molecule is the sum of the branches found in step 4 7) The number of alkyl branches per 100 carbon atoms is the number of branches per molecule (step 6) x 100 / average 8) Estimate the branching index (BI) by ¹ H NMR analysis, calculated from the number of carbons, which is methyl hydrogen in the total hydrogen as estimated by NMR in the liquid hydrocarbon composition (chemical shift range 0 9) Estimated Branch Proximity (BP) by ¹³ C NMR, which is given as a percentage of repetitive methylene carbons—this is NMR in liquid hydrocarbon compositions Is 4 or more carbons away from the terminal group or branch (represented by the NMR signal at 29.9 ppm) in the total carbon as estimated in. This measurement can be performed using an arbitrary Fourier transform NMR spectrometer, for example, one having a magnet larger than 7.0 T. After confirmation by mass spectrometry, the absence of aromatic carbon was investigated by UV or NMR, and the spectral width for ¹³ C NMR test was a saturated carbon region of 0-80 ppm relative to TMS (tetramethylsilane). It can be limited to. A 25-50 wt% solution in chloroform-dl was excited with a 30 ° pulse and then with a 1.3 second (sec) acquisition time. In order to minimize non-uniform intensity data, broadband proton reverse-gated decoupling is used during the 6 second delay before the excitation pulse and during acquisition. The sample is doped with 0.03 to 0.05 M Cr (acac) ₃ (Tris (acetylacetonato) -chromium (III) as a relaxation agent to ensure sufficient strength observation. The DEPT and APT sequences are It can be performed according to the literature description with small deviations described in the Varian or Bruker operating manual DEPT is a Distortionless enhancement by Polarization Transfer DEPT45 sequence Signals all attached carbons, DEPT90 shows only CH carbon, DEPT135 shows CH, and CH ₃ above, and CH ₂ 180 degrees outside (bottom) of phase. Known in the field Bond proton test, which allows all the carbon to be seen, but when CH and CH ₃ are above, quaternary and CH ₂ are below. Using the assumption in the calculation that the sample is iso-paraffinic, it can be determined by ¹³ C NMR The content of unsaturation can be measured using field ionization mass spectrometry (FIMS).

  In one embodiment, the metalworking fluid includes a number of components in the base oil matrix, including optional additives.

  Base oil matrix component. In one embodiment, the matrix-forming base oil or blend thereof is by isomerization of the product itself, a fraction thereof, or a waxy feedstock (“Fischer-Tropsch derived base oil”) derived from a Fischer-Tropsch process. It contains at least one isomerized base oil that originates from or is produced in some stages. In another embodiment, the base oil comprises an isomerized base oil made from at least one substantially paraffinic wax feed (“waxy feed”). In a third embodiment, the base oil consists mainly of at least one isomerized base oil.

  Fischer-Tropsch derived base oils include, for example, U.S. Pat. Nos. 6,080,301, 6,090,909, and 6,165,949, and U.S. Patent Publication Nos. 2004 / 0079678A1, 2005/0133409, and 2006/0289337. Is disclosed in many patent publications, including The Fischer-Tropsch process is a catalytic chemical reaction in which carbon monoxide and hydrogen are liquids in various forms including light reaction products and waxy reaction products, both of which are substantially paraffinic. Converted to hydrocarbon.

In one embodiment, the isomerized base oil has a sequential number of carbon atoms and less than 10% by weight naphthenic carbon by ndM. In yet another embodiment, the isomerized base oil produced from the waxy feed has a kinematic viscosity at 100 ° C. of 1.5 to 3.5 mm ² / s.

  In one embodiment, the isomerized base oil is produced by a process in which hydroisomerization dewaxing is performed under conditions sufficient for the base oil to have: a) at least one of less than 0.03 Weight percent of all molecules with aromatic functionality; b) weight percent of all molecules with at least one cycloparaffinic functionality greater than 10; c) weight percent of molecules with monocycloparaffinic functionality greater than 20. Ratio of molecular weight percent with multicycloparaffin functionality; d) 28 × Ln (kinematic viscosity at 100 ° C.) + Viscosity index greater than 80.

In another embodiment, the isomerized base oil is highly paraffinic using a shape selective intermediate pore size molecular sieve comprising a noble metal hydrogenation component and under conditions of 600 to 750 ° F. (315-399 ° C.). It is produced from a process in which system waxes are hydroisomerized. In this process, the hydroisomerization conditions were 10% by weight for the conversion of compounds boiling above 700 ° F. (371 ° C.) in the waxy feed to compounds boiling below 700 ° F. (371 ° C.). To be maintained at 50% by weight. The resulting isomerized base oil has a kinematic viscosity at 100 ° C. of 1.0 to 3.5 mm ² / s and a Noack volatility of less than 50% by weight. The base oil contains more than 3% by weight of molecules with cycloparaffinic functionality and less than 0.30 weight percent of aromatic compounds.

In one embodiment, the isomerized base oil has a Noack volatility less than the amount calculated by the formula: 1000 × (kinematic viscosity at 100 ° C.) ^−2.7 . In another embodiment, the isomerized base oil has a Noack volatility less than the amount calculated by the following formula: 900 × (kinematic viscosity at 100 ° C.) ^−2.8 . In a third embodiment, the isomerized base oil has a kinematic viscosity at 100 ° C. of greater than 1.808 mm ² / s and a Noack volatility less than the amount calculated by the following formula: 1.286 + 20 (kv100) ^−1.5 + 551.8e ^−kv100 (where kv100 is the kinematic viscosity at 100 ° C.). In the fourth embodiment, the isomerized base oil has a kinematic viscosity of less than 4.0 mm ² / s at 100 ° C., and a Noack volatility weight percent from 0 to 100. In a fifth embodiment, the isomerized base oil has a kinematic viscosity of 1.5 to 4.0 mm ² / s and a Noack volatility that is less than the Noack volatility calculated by the following formula: 160-40 ( Kinematic viscosity at 100 ° C).

In one embodiment, the isomerized base oil has a kinematic viscosity in the range of 2.4 to 3.8 mm ² / s at 100 ° C. and a Noack volatility less than the amount defined by the following formula: 900 × ( Kinematic viscosity at 100 ° C) ^-2.8-15 ). For a kinematic viscosity in the range of 2.4 to 3.8 mm ² / s, the formula: 900 × (kinematic viscosity at 100 ° C.) ^−2.8 −15) is Give a Noack volatility lower than kinematic viscosity).

In one embodiment, the isomerized base oil is such that the base oil has a kinematic viscosity of 3.6 to 4.2 mm ² / s at 100 ° C., a viscosity index of greater than 130, a Noack volatility weight percentage of less than 12, and less than −9 ° C. Is produced from a process in which highly paraffinic wax is hydroisomerized under conditions having a pour point of

In one embodiment, the isomerized base oil has the formula: AIT the (℃) = 1.6 × (kinematic viscosity at ^{40 ℃, mm 2 / s)} +300 exceeds the defined AIT in autoignition temperature (AIT) Have. In a second embodiment, the base oil has an AIT greater than 329 ° C. and a viscosity index greater than 28 × Ln (kinematic viscosity at 100 ° C., mm ² / s) +100.

In one embodiment, the isomerized base oil has a relatively low traction coefficient, in particular the traction coefficient is the formula: traction coefficient = 0.000 × Ln (kinematic viscosity in mm ² /s)−0.001 (Here, the kinematic viscosity in the formula is the kinematic viscosity during the traction coefficient measurement and is 2 to 50 mm ² / s) and is less than the amount calculated. In one embodiment, the isomerized base oil has a traction coefficient of less than 0.023 (or less than 0.021) as measured by a kinematic viscosity of 15 mm ² / s and a ratio of slide to 40% rotation. In another embodiment, the isomerized base oil has a viscosity index greater than 150, and a traction coefficient less than 0.015, as measured by a kinematic viscosity of 15 mm ² / s and a ratio of slide to 40 percent rotation.

  In some embodiments, isomerized base oils having a low traction coefficient also exhibit a relatively high kinematic viscosity and a relatively high boiling point. In one embodiment, the base oil has a traction coefficient less than 0.015 and a 50 wt% boiling point greater than 565 ° C (1050 ° F). In another embodiment, the base oil has a traction coefficient less than 0.011 and a 50 wt% boiling point greater than 582 ° C. (1080 ° F.) according to ASTM D6352-04.

  In some embodiments, an isomerized base oil having a low traction coefficient has a branch index of less than or equal to 23.4, a branch proximity of greater than or equal to 22.0, and a free carbon index of 9 to 30 (Free Carbon). The intrinsic branching characteristics by NMR, including Index) are also shown. In one embodiment, the base oil has at least 4 wt% naphthenic carbon, and in another embodiment, at least 5 wt% by ndM analysis according to ASTM D3238-95 (2005 reapproved). Of naphthenic carbon.

In one embodiment, the isomerized base oil has an intermediate oil isomer comprising a paraffinic hydrocarbon component, wherein the degree of branching is less than 7 alkyl branches per 100 carbons, and the base oil is branched. Of alkyl branches of less than 8 per 100 carbons and less than 20% by weight of the alkyl branches comprising a paraffinic hydrocarbon component in the 2-position. In one embodiment, the FT base oil is calculated by the pour point below −8 ° C .; the kinematic viscosity at 100 ° C. of at least 3.2 mm ² / s; and the formula = 22 × Ln (kinematic viscosity at 100 ° C.) + 132 The viscosity index exceeds the viscosity index.

  In one embodiment, the base oil has a total molecule having a cycloparaffinic functionality of greater than 10% and less than 70% by weight and a molecular weight percent of monocycloparaffinic functionality greater than 15 to multicycloparaffins. Includes a ratio of molecular weight percent with functionality.

In one embodiment, the isomerized base oil has an average molecular weight of 600 to 1100 and an average degree of branching in the molecule of 6.5 to 10 alkyl branches per 100 carbon atoms. In another embodiment, the isomerized base oil has a kinematic viscosity of about 8 to about 25 mm ² / s and an average degree of branching in the molecule of 6.5 to 10 alkyl branches per 100 carbon atoms.

In one embodiment, the isomerized base oil comprises a total weight percent of molecules having a cycloparaffinic functionality greater than 10 and a weight percent of molecules having a monocycloparaffinic functionality greater than 15 versus multicycloparaffins. Obtained from a process in which highly paraffinic waxes are hydroisomerized at a hydrogen to feed ratio of 712.4 to 3562 liters H ₂ / liter oil to have a weight percent ratio of functional molecules. In another embodiment, the base oil has a viscosity index that exceeds the amount defined by the formula: 28 × Ln (kinematic viscosity at 100 ° C.) + 95. In a third embodiment, the base oil has an aromatic weight percent less than 0.30; a molecular weight percent with a cycloparaffinic functionality greater than 10; a molecular weight percent with a monocycloparaffinic functionality greater than 20. Ratio of molecular weight percent with multicycloparaffinic functionality; and a viscosity index greater than 28 × Ln (kinematic viscosity at 100 ° C.) + 110. In a fourth embodiment, the base oil further has a kinematic viscosity of greater than 6 mm ² / s at 100 ° C. In a fifth embodiment, the base oil has an aromatic weight percent less than 0.05 and a viscosity index greater than 28 × Ln (kinematic viscosity at 100 ° C.) + 95. In a sixth embodiment, the base oil has an aromatic weight percent less than 0.30, a molecular weight percent with cycloparaffinic functionality greater than a kinematic viscosity at 3 × 100 ° C. (mm ² / s), And a ratio of molecules with monocycloparaffinic functionality to molecules with multicycloparaffinic functionality greater than 15.

In one embodiment, the isomerized base oil comprises 2 to 10% naphthenic carbon as measured by ndM. In one embodiment, the base oil has a kinematic viscosity of 1.5-3.0 mm ² / s at 100 ° C. and 2-3% naphthenic carbon. In another embodiment, it has a kinematic viscosity at 100 ° C. of 1.8-3.5 mm ² / s and 2.5-4% naphthenic carbon. In 3rd Embodiment, it has 3-6 mm < ² > / s kinematic viscosity and 2.7-5% of naphthenic carbon at 100 degreeC. In a fourth embodiment, it has a kinematic viscosity of 10-30 mm ² / s at 100 ° C. and a naphthenic carbon greater than 5.2%.

  In one embodiment, the isomerized base oil has an average molecular weight greater than 475; a viscosity index greater than 140, and an olefin weight percent less than 10. When incorporated into a metalworking fluid, the base oil improves the defoaming and low foaming properties of the mixture.

In one embodiment, the isomerized base oil, at 100 ° C. ^{2 mm} from the 2 / s kinematic viscosity ^{6 mm} 2 / s; 2300 MPa at -35 ° C.; ^{7 mm} 2 / s from 20 mm ² / s kinematic viscosity at 40 ° C.. CCS viscosity below s; pour point in the range of −20 to −40 ° C .; molecular weight in the range of 300-500; density in the range of 0.800 to 0.820; paraffin carbon in the range of 93-97%; 3-7% A FT base oil having a Noack volatility of 8 to 20% by weight as measured by ASTM D5800-05 Procedure B.

Another In embodiments, the isomerized base oil has a kinematic viscosity of ^{3 mm} 2 / s from ^{2 mm} 2 / s at 100 ° C. for mist suppressant performance; at 40 ° C. from ^{7 mm} 2 / s of 25 mm ² / s kinematic viscosity; A viscosity index of 120 to 150; a pour point in the range of −20 to −50 ° C .; a molecular weight of 300 to 500; a density in the range of 0.800 to 0.820; a paraffinic carbon in the range of 92 to 97%; FT base oil with a “light” range viscosity having a Naack volatility of 8 to 60% by weight measured according to ASTM D5800-05 Procedure B; It is. In another embodiment, the isomerized base oil has a kinematic viscosity of ^{7 mm} 2 / s from ^{5 mm} 2 / s at 100 ° C., a viscosity index of 140 to 160; kinematic viscosity at 40 ° C. from 25mm ² / s 50mm ² / s Pour point in the range of −15 to −25 ° C .; molecular weight in the range of 450 to 550; density in the range of 0.820 to 0.830; “medium” range viscosity with paraffinic carbon in the range of 90 to 95% FT base oil. In a third embodiment, the base oil comprises a mixture of “light” and “medium” range viscosity FT base oils.

  In one embodiment, the metalworking fluid uses at least one of the above isomerized base oils. In another embodiment, the composition consists primarily of at least a Fischer-Tropsch base oil. In yet another embodiment, the metalworking fluid is defined in at least one isomerized base oil as a base oil matrix, and optionally 5 to 95 wt% of at least another type of oil, such as APT exchange guidelines. As such, lubricating base oils selected from Group I, II, III, IV, V, and VI lubricating base oils, and mixtures thereof are used. In a fourth embodiment, the metalworking fluid uses an isomerized base oil and 5 to 20% by weight of at least another type of oil. Examples include conventionally used mineral oils, synthetic hydrocarbon oils or synthetic ester oils, or mixtures thereof depending on the application. The mineral lubricant base stock can be any conventionally refined base stock derived from paraffin, naphthene and mixed base crudes. Synthetic lubricating oils that can be used include esters of glycols and complex esters. Other synthetic oils that can be used include synthetic hydrocarbons, such as polyalphaolefins; alkylbenzenes (eg, alkylate residuals derived from alkylation of benzene with tetrapropylene, or copolymers of ethylene and propylene); silicone oils (eg, , Ethyl phenyl polysiloxane, methyl polysiloxane, etc.), polyglycol oil (for example, obtained by condensing butyl alcohol with propylene oxide) and the like. Other suitable synthetic oils include polyphenyl ethers (eg, those having 3 to 7 ether linkages and 4 to 8 phenyl groups). Other suitable synthetic oils include polyisobutenes and alkylated aromatic compounds such as alkylated naphthalene.

  Additional components: The metalworking fluid in one embodiment is characterized as having reduced mist formation, lower foaming, and good defoaming properties compared to prior art compositions. Depending on the application, eg straight oil (neat oil) or soluble oil, metalworking fluids are known in the art to improve the properties of their compositions in amounts ranging from 0.10 to 40% by weight. Available additives may be included. These additives include: metal deactivators; corrosion inhibitors; antibacterial agents; anticorrosives; emulsifiers; couplers; extreme pressure agents; friction-resistant materials; rust inhibitors; Preservatives; antioxidants; chelating agents (such as edetate); pH adjusters; antiwear agents (including active sulfur antiwear additive packages); metalworking that includes at least one of the aforementioned additives A fluid additive package is included.

  In different embodiments, any anti-mist additive in the prior art (for metalworking fluids consisting primarily of a base oil matrix comprising an isomerized base oil and at least one additive other than anti-mist / antifoam agent ( There is no need to add a mist inhibitor or a mist inhibitor) or an antifoaming material. However, in other embodiments and depending on the end use application, a small amount of an additive such as a mist inhibitor, in one embodiment 0.05 to 5.0% by volume, and in other embodiments 1 wt. Optionally, an amount in the range of less than% may be added. Non-limiting examples include rhamsan gum, hydrophobic and hydrophilic monomers, styrene or hydrocarbyl-substituted styrene hydrophobic monomers and hydrophilic monomers, oil solubility in the range of about 300,000 to over 4 million molecular weight (viscosity average molecular weight) Organic polymers (isobutylene, styrene, alkyl methacrylate, ethylene, propylene, n-butylene vinyl acetate, etc.) are included. In one embodiment, polymethylmethacrylate or poly (ethylene, propylene, butylene or isobutylene) with a molecular weight range of 1 to 3 million is used.

  In some embodiments and for certain applications, small amounts of prior art antifoam agents can also be added to the present compositions in amounts ranging from 0.05 to 15.0% by weight. Non-limiting examples include polydimethylsiloxanes (often trimethylsilyl terminated), alkyl polymethacrylates, polymethylsiloxanes, N-acyl amino acids having long chain acyl groups and / or their salts, (alkyl alkylene oxides and / or acyls) N-alkyl amino acids having long-chain alkyl groups and / or their salts (used simultaneously with alkyl oxides), acetylenic diols and ethoxylated acetylenic diols, silicones, hydrophobic materials (eg silica), fatty amides, fatty acids, fatty acids Esters and / or organic polymers, modified siloxanes, polyglycols, esterified or modified polyglycols, polyacrylates, fatty acids, fatty acid esters, fatty alcohols, fatty alcohol esters, oxo-alcohols, fluoro fields Active agent, a wax (ethylenebis scan tele amide wax, polyethylene wax, polypropylene wax, ethylene bis-scan tele amide wax, and paraffin wax), are included Ureumu. Antifoaming agents can be used with suitable dispersing and emulsifying agents. Additional active foam inhibitors are described by Henry T. et al. Kerner (Noyes Data Corporation, 1976), pages 125-162, described in “Foam Control Agents”.

  In various embodiments, the metalworking fluid further comprises a lubricant including overbased sulfonates, sulfurized olefins, chlorinated paraffins and olefins, sulfurized ester olefins, amine-terminated polyglycols, and dioctyl sodium phosphate salts. . In yet other embodiments, the composition further comprises a corrosion inhibitor comprising a carboxylic acid / boric acid diamine salt, a carboxylic acid amine salt, an alkanolamine, an alkanolamine borate, and the like.

In various embodiments, the metalworking fluid further comprises an oil soluble metal deactivator in an amount of 0.01 to 0.5 volume% (based on the volume of the final oil). Non-limiting examples include triazoles or thiadiazoles, in particular aryl triazoles (such as benzotriazole and tolyltriazole), alkyl derivatives of such triazoles, and benzothiadiazole (R (C ₆ H ₃ ) N ₂ S, where R is H or C ₁ to C ₁₀ alkyl). Suitable materials are available from Ciba Geigy under the Irgamet and Reomet trademarks or from Vanderbilt Chemical Corporation under the Vanlube trademark.

  In one embodiment, a small amount of at least one antioxidant ranging from 0.01 to 1.0% by weight is used, such as when the composition serves the dual purpose of cutting fluid and machine lubricant. obtain. Non-limiting examples include antioxidants of amine or phenol type, or mixtures thereof, such as butylated hydroxytoluene (BHT), bis-2,6-di-t-butylphenol derivatives, sulfur-containing hindered phenols. , And sulfur-containing hindered bisphenols.

  In some embodiments, the metalworking fluid further comprises 0.1 to 20% by weight of at least one extreme pressure agent. Non-limiting examples of extreme pressure agents include zinc dithiophosphate, molybdenum oxysulfide dithiophosphate, molybdenum oxysulfide thiocarbamate, molybdenum amine compounds, sulfurized oils and fats, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides Thiocarbamate, thioterpene, dialkyl thiodipropionate and the like.

  In addition to the above additives, various other conventional additives can be added to the extent that they do not interfere with the action of the metalworking fluid. Examples include fatty acids and their salts; polyhydric alcohols (propylene glycol, glycerin, butylene glycerol, etc.); surfactants (anionic surfactants, amphoteric surfactants, nonionic surfactants, etc.); and interfaces Boron nitride dispersed in a dispersing agent such as activity is included.

  Manufacturing Method: The optional additives used in formulating the metalworking fluid composition can be blended into the base oil matrix individually or in various sub-combinations. In one embodiment, all of the ingredients are blended simultaneously using an additive concentrate (ie, additive plus diluent, such as a hydrocarbon solvent). The use of additive concentrates takes advantage of the mutual compatibility afforded by the combination of ingredients when in the form of additive concentrates.

  In another embodiment, the metalworking fluid may be optionally mixed with a base oil matrix at a suitable temperature, eg, about 60 ° C., until uniform for use as a straight oil cutting fluid. Prepared by mixing with additive package (s). In yet another embodiment, an emulsifier may be added to the metalworking fluid to form an oil-in-water emulsion.

  Properties: In one embodiment, the metalworking fluid composition is characterized as having reduced mist formation, low foaming and excellent defoaming properties. The foaming degree of the metalworking fluid can be measured using the ASTM D892-95 foam test. In one embodiment, the metalworking fluid exhibits a Sequence II foaming foam height of less than 50 mL when evaluated under the ASTM D892-06 method. In yet another embodiment, the metalworking fluid exhibits a Sequence II foam height of less than 40 mL. In a third embodiment, the sequence II foam height is less than 30 mL. In a fifth embodiment, the sequence II foam height is less than 20 mL. In 6th Embodiment, it cannot measure at all (0 mL).

  In one embodiment, the metalworking fluid exhibits a Sequence I foaminess of less than 100 mL according to ASTM D892-03. In another embodiment, the fluid has a Sequence I foaming rate of less than 50 mL. In a third embodiment, it has a Sequence I foaming rate of less than 30 mL.

  In one embodiment, the metalworking fluid has a numerical value according to ASTM D1401-02 that results in a 3 mL emulsion at 54 ° C. equal to or less than 30. In yet another embodiment, the fluid has a numerical value according to ASTM D1401-02 that is a 3 mL emulsion at 82 ° C. equal to or less than 60.

  Defoaming can be measured using the ASTM D3427 (2003) method for petroleum bubble separation time and measures the fluid's ability to separate the trapped gas. In one embodiment, the metalworking fluid has a defoaming time measured at 50 ° C. of less than 0.60 minutes as measured according to ASTM D3427 (2003). In a second embodiment, it has a defoaming time of less than ½ minute.

In one embodiment, the metalworking fluid exhibits reduced mist formation and provides aerosol or particle control to the fluid, eg, 5 to 50 compared to a metalworking fluid comprising, for example, prior art base oil group I. % Mist reduction. Mist reduction experiments were performed by Marano et al., Journal of the Society of Tribologists and Lubricating Engineers, October 1995, page 25-35, "Polymer Additives Mist animist Mist addict Mist Add mist Mist Incipients Mist Incipients Mist Inhibitors." It can be measured according to the same aerosol (mist) formation test as described in “Fluids”. In one embodiment, the metalworking fluid with no added anti-mist additive has an average mist accumulation rate of less than 300 mg / mm ³ in the first 30 seconds (after initiation) of the aerosol mist formation test. In another embodiment, the metalworking fluid without any mist additive has an average mist accumulation rate of less than 250 mg / mm ³ in the first 30 seconds of the aerosol mist formation test. In a third embodiment, the average mist accumulation rate is less than 200 mg / mm ³ in the first 30 seconds of the test. In a fourth embodiment, the average mist accumulation rate is less than 150 mg / mm ³ in the first 60 seconds of the test.

In one embodiment, the metalworking fluid composition is readily biodegradable and its base oil has an OECD 301D ranging from 30 to 95%. In one embodiment, the metalworking fluid has a kinematic viscosity of 10-14 mm ² / s at 40 ° C. and an OECD 301D biodegradability of ≧ 60%. In a second embodiment, the composition has a kinematic viscosity at 40 ° C. of less than 10 mm ² / s and OECD 301D biodegradability of ≧ 80%. In a third embodiment, the composition has a kinematic viscosity at 40 ° C. of less than 8 mm ² / s and an OECD 301D biodegradability of ≧ 90%. In a fifth embodiment, the metalworking fluid is at least 30% biodegradable as measured according to ODCE301D.

  Metalworking fluids can be characterized as appropriate or inappropriate for extreme pressure applications. Fluids that are considered suitable for extreme pressures are those that prevent sliding metal surfaces from sticking under extreme pressure conditions. The sticking of the metal surface is due to friction between the opposing surface roughnesses. Surface roughness is a microscopic protrusion on a metal surface that results from a metalworking operation. One approach to measuring the extreme pressure characteristics of a fluid is to measure the loading force between the sliding surfaces that can be sustained by the lubricant without sticking of the sliding surfaces. Such an approach is described as a Falex load test, which is an ASTM standard test for fluid lubricants (ASTM D-3233 (2003)). In one embodiment, the metalworking fluid is characterized as having a Falex reference wear of less than 10 teeth. In another embodiment, it is characterized as having a Falex reference load greater than about 4,500 pounds force.

  In one embodiment, the metalworking fluid is characterized as having excellent lubricating properties, particularly a lubricating surface in sliding contact, as measured in a four-ball wear test according to ASTM D4172-94 (2004) e1. In one embodiment, the metalworking fluid has a four ball wear scar diameter of less than about 0.07 mm.

  In some applications, and with the use of isomerized base oils with low kinematic viscosity, metalworking fluids are characterized as having a smooth liquid flow for good pump circulation. Furthermore, the metal working fluid has good properties that can prevent frictional heat from being generated between the tool and the workpiece, thereby increasing the effective tool life.

  Applications: In one embodiment, metalworking fluids are used in the production of semiconductors, plant equipment, and automotive parts, where the shape of the final object (eg, silicon wafer or mechanical part) is a progressive metal or silicon Obtained with or without selective removal. Non-limiting examples of operations include cutting, drilling, drilling, honing, broaching, grinding, forming, stamping, casting, forging, rolling, drilling, (money) casting, drawing, press forming, deburring, grinding Grooving, tapping, chamfering, broaching, reaming, honing, lapping, distortion correction, and drawing.

  In one embodiment of the metal work, the metal working fluid is applied to the contact portion between the tool and the workpiece. The fluid impregnates the contact portion in the fluid, sprays the fluid into the contact portion, overflows the contact portion with the fluid, pumps the flow of fluid into the contact portion, lubricates the tool or workpiece with the lubricating fluid It can be applied by a variety of methods, including any means of periodically moistening or applying the lubricant constantly or intermittently in the contact area between the tool and the workpiece.

  Unless otherwise noted, the compositions are prepared by mixing the components in the amounts shown in the examples / tables. The components used in the examples are described below.

  The EP agent is a commercially available sulfurized polymerized ester, 10% inert sulfur extreme pressure agent.

  HYNAP ™ N100 HTS hydrotreated, naphthenic oil (Group V) is available from San Joaquin Refining Oil, Inc. , Bakersfield, CA.

  Ashland ™ 100SN Group I oil is available from Ashland Inc. Is provided.

  Chevron ™ 100R Group 2 oil, Chevron ™ 100R Group 3 oil, and Chevron Synfluid 4 cSt PAO oil are all provided by Chevron Corporation, San Ramon, CA.

  Additive 2 is a sulfurized vegetable fatty acid ester. The defoamer is an acrylate oligomer antifoam / defoamer. Additive CAS is a commercially available overbased calcium sulfonate PEP metalworking additive containing carbonated alkyl benzene sulfonate. The additive SO is a sulfurized olefin.

Seal oil (MSO) having a viscosity of 3.39 mm ² / sec at 40 ° C., and base stock SN100 (density of 0.864 and viscosity of 20.6 mm ² / sec at 40 ° C.), SN 150 and SN 600 (API group) I) is commercially available from a number of suppliers.

  GTL Fischer-Tropsch derived base oil GST0449, FTBO L, FTBO XL, FTBO XXL, and FTBO M are available from Chevron Corp. Is provided. The properties of the Fischer-Tropsch derived base oil used in the examples are shown in Table 3.

  Anti-mist agent 1 is a methacrylate copolymer. Anti-mist agent 2 is a commercially available high molecular weight oil-soluble polymer tackifier.

(Example 1 to Example 6)
Several metalworking fluid compositions having ingredients as described in Table 1 were formulated and their properties were measured using various standard test methods: ASTM D1401 for water separability of petroleum and synthetic fluids -02; ASTM D3427 (2003) Standard Test Method for Petroleum Defoaming; and ASTM D892-95 Foam Stability Sequence Test. As shown in the table, the examples incorporating the isomerized base oil show low foaming (no foam height) and defoamability comparable to, if not better than, prior art oils (1 minute) In terms of test reproducibility).
Table 1

(Example 7 to Example 13)
Several metalworking fluid compositions having ingredients as described in Table 2 were formulated and their properties measured / recorded. Examples 11 to 13 each compare compositions with addition of 0.25 wt% mist inhibitor (high molecular weight oil soluble polymer tackifier).

Samples were added as a mist suppressor as a mist suppressor mist additive as a mist inhibitor in metal cutting fluids, Oct. 1995, page 25-35, Journal of the Society of Tribologists and Lubricating Engineers. The same aerosol (mist) formation experiment as described in “ In the test, the metalworking fluid (in a 100 mL sample) was fed at a constant flow rate of up to 0.0084 liter / min through a tube (eg, ID 0.0011 m) to the tip of the coaxial atomizer at a constant flow rate of up to 0.0084 liter / min. Compressed air was supplied through a ring between the outer and inner tubes (ID 0.0021 m and OD 0.0013 m, respectively) at a flow rate of up to 35 liters / minute. The mist generated by the atomizer was sent to a long and wide plexiglass duct with a square cross section or chamber (eg, 12 inch × 12 inch × 18 inch chamber). The amount of mist generated as a function of time (as mg / mm ³ over 5 minutes) was captured and recorded with a datalogger. In these experiments, a portable real-time aerosol monitor DataRAM® [MIE Instruments Inc. Bedford Mass. ] Was used as a data logger to quantitate the generated mist concentration continuously. DataRAM is a nepheline monitor used to measure the concentration of particles in the air by sensing the amount of light scattered by a population of particles passing through the sampling space.

  For all of the samples, most mist occurred at the beginning of the test. After spraying, the mist tended to fall to the bottom of the container, thus indicating a drop in the amount of mist collected.

表３

The measured values of the aerosol (mist) formation experiment are plotted in FIGS. 1 to 3 as a function of time. The results generally indicate that metalworking fluids containing Fischer-Tropsch derived base oils result in significantly less mist formation than prior art base oils, and the reduction in mist formation is at least in the first 30 seconds of the aerosol mist formation test. From 10% (in some examples) to over 75%. Example 10 with isomerized base oil performed better (with reduced mist formation) compared to Example 9 with mineral croup I base oil and an additional 2 wt% anti-mist additive. In FIG. 3, all examples (Examples 11 to 13) with high molecular weight oil soluble polymer tackifier added as a powerful (and expensive) anti-mist additive show comparable performance.
Table 2

Table 3

  Unless otherwise stated, for the purposes of this specification and the appended claims, all numbers representing amounts, percentages or ratios, and all other numbers used in this specification and claims are used. Should be understood to be modified in all cases by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained with the present invention. As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless expressly and explicitly limited to one referent. It is noted that the target object is included. As used herein, the term “include” and grammatical variations thereof are intended to be non-limiting, and thus the list of items in a list may be substituted or Do not exclude other similar items that may be added to the list items.

  This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope is defined in the claims, and may include other examples that occur to those skilled in the art. Such other embodiments may have equivalent structural elements that have structural elements that differ from the literal terms of the claims or that have substantive differences from the literal terms of the claims. If included, it is intended to be within the scope of the claims.

Claims (15)

Lubricating base oils having sequential numbers of carbon atoms and less than 10 wt% naphthenic carbon by ndM; and metalworking fluid additive packages; metal deactivators; corrosion inhibitors; antibacterial agents; Extreme pressure agent; Anti-friction agent; Rust preventive agent; Polymeric substance; Anti-inflammatory agent; Bactericidal agent; Antiseptic agent; Antioxidant; Chelating agent such as edetate; A metalworking fluid comprising 0.10 to 10% by weight of at least one additive selected from the group consisting of:
A metalworking fluid, wherein the metalworking fluid has a defoaming property of less than 0.6 minutes at 50 ° C. according to ASTM D3427-03 and a Sequence II foaming rate of less than 50 mL according to ASTM D892-03.   The metalworking fluid according to claim 1, wherein the defoaming property at 50 ° C is less than 0.5 minutes.   The metalworking fluid according to claim 1 or 2, wherein the sequence II foaming rate is less than 40 mL according to ASTM D892-03.   The metalworking fluid according to any one of claims 1 to 3, wherein the foaming degree of Sequence II is less than 20 mL according to ASTM D892-03.   5. The metalworking fluid according to any one of claims 1 to 4, wherein the metalworking fluid has a biodegradability of at least 30% as measured according to OECD301D.   6. The metalworking fluid according to any one of claims 1-5, wherein the metalworking fluid further has a Sequence I foaming rate of less than 50 mL according to ASTM D892-03.   7. The metalworking fluid according to any one of claims 1-6, wherein the metalworking fluid has a numerical value according to ASTM D1401-02 that becomes a 3 mL emulsion of less than 30 at 54 ° C.   The metalworking fluid according to any one of claims 1 to 7, wherein the lubricating base oil is a Fischer-Tropsch derived base oil produced from a waxy raw material. The Fischer - Tropsch derived base oil, at 100 ° C. ^{2 mm} from the 2 / s kinematic viscosity ^{6 mm} 2 / s; 2300 MPa at -35 ° C.; ^{7 mm} 2 / s from 20 mm ² / s kinematic viscosity at 40 ° C.. CCS viscosity below s; pour point in the range of −20 to −40 ° C .; molecular weight in the range of 300 to 500; density in the range of 0.800 to 0.820; paraffinic carbon in the range of 93 to 97%; 1 to 8 having a Noack volatility of 8 to 20% by weight as measured by ASTM D5800-05 Procedure B; The metal working fluid according to one item.   10. The lubricating base oil according to any one of claims 1 to 9, wherein the lubricating base oil comprises an isomerized base oil and 5 to 20% by weight of at least one mineral oil, synthetic hydrocarbon oil or synthetic ester oil and mixtures thereof. Metal working fluid according to   11. The lubricating base oil according to any one of claims 1 to 10, wherein the lubricating base oil has an average molecular weight of 600 to 1100, and an average degree of branching in the molecule with 6.5 to 10 alkyl branches per 100 carbon atoms. The metalworking fluid described. The lubricating base oil has a Noack volatility weight percent of 0 to 100, an auto-ignition temperature (AIT) exceeding the amount specified by 1.6 × (kinematic viscosity at 40 ° C., mm ² / s) +300, The metal working fluid according to any one of claims 1 to 11. The lubricating base oil (kinematic viscosity at ^{100 ℃, mm 2 / s)} 28 × Ln +300 having a viscosity index of greater than, metalworking fluids according to any one of claims 1 to 12.   The ratio of the molecular weight percent with monocycloparaffinic functionality to the molecular weight percent with multicycloparaffinic functionality greater than 15 and the molecular weight percent with multicycloparaffinic functionality greater than 15; 14. A metalworking fluid according to any one of claims 1 to 13 having a ratio of molecular weight percent with monocycloparaffinic functionality. When the lubricating base oil is measured with a total molecule with cycloparaffinic functionality greater than 10% and less than 70% by weight, and a kinematic viscosity of 15 mm ² / s and a ratio of slide to 40% of rotation. 15. A metalworking fluid according to any one of claims 1 to 14, having a traction coefficient of less than 023.

Images