Use for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient

0001The present invention relates to the operation of large low speed, medium speed and high speed engines using an additive lubricant formulation (or an additive lubricant formulation).

0002Diesel engines designed for marine and fixed power applications can be either two-stroke or four-stroke with 20 or less cylinders and are typically classified as low speed, medium speed or high speed diesel engines. To. These engines burn a wide variety of fuels ranging from residual fuel oil or heavy oil to natural gas (diesel compression or spark ignition), marine propulsion, marine assistance (ship power generation), distributed power generation, and combined heat and power (CHP). Most commonly used for Lubrication of such an engine can be total loss (ie, lubricating oil supplied directly to the cylinder by cylinder oil) or recirculation with a reservoir. Lubrication of critical engine components includes piston rings, cylinder liners, bearings, piston cooling, fuel pumps, engine control hydraulics and the like. Fuel is typically the main cost of operating these engines, and the typical 12-cylinder, 90 cm caliber low-speed diesel engine used for shipping container transport is up to about $ 33 M / year at today's price of $ 480 / MT. Will burn heavy oil. Therefore, a fuel efficiency gain as low as 1% will bring shipowners an annual savings of up to about $ 330k. In addition, government agencies such as the International Maritime Organization, the US Environmental Protection Agency, and the California Air Resources Board have enacted emissions regulations for these engines. Inside. Improving fuel efficiency is a corresponding emission (CO₂, SO_x, NO_xAnd particulate matter), which should bring some emissions trading value.

0003In addition to providing sufficient oil film thickness to prevent metal-metal contact, the lubricating oils for these engines contain sulfur to minimize corrosion wear on piston rings and cylinder liners. Neutralizing the acids formed by fuel combustion, minimizing engine deposits formed by fuel combustion and by contamination of lubricating oil with raw or partially burned fuel, extremes in these engines It is designed to deal with a variety of other stresses, including resisting the thermal / oxidative decomposition of thermal lubricants, transferring heat from the engine, and so on.

0004A long-term requirement is that the lubricant must maintain its cleanliness in the high temperature environment of the engine, especially with respect to critical components such as pistons and piston rings. Contamination of engine oil in the engine due to the accumulation of heat / oxidative decomposition products of raw and partially burned fuel combustion products, water, soot and oil itself in the engine can degrade the engine cleanliness performance of the engine oil. Therefore, it is desirable that engine oils be formulated to have good cleanliness qualities and to resist the deterioration of their qualities due to contamination and thermal / oxidative decomposition.

0005Patent Document 1 includes a liquid oil-miscible polyisobutylene (PIB) and a cleaning agent, preferably one or more of hyperbasic phenolate, phenylate, salicylate or sulfonate, an antioxidant, an anti-wear agent and a dispersant. Medium Heavy Group I or Group II Neutral Base Oil in Combination with Additive Package, typically 300-500-600 SUS (approx. 12 mm)²For diesel engine cylinder oil with improved cleanliness and load capacity and reduced port deposit characteristics for use in marine and fixed low speed diesel engines, including KV) at 100 ° C below / sec. Finished lubricating oil has a range of 15 to 25 mm²It has a total base value of KV at 100 ° C / sec and a range of 40-100 mg KOH / g.

0006The subject of Patent Document 2 is a gas engine oil with an improved life as evidenced by the increased resistance of the oil to oxidation, nitrification and deposit formation. The gas engine oil of the patent has a major amount of base oil with a lubricating viscosity, at least one alkaline or alkaline earth metal salt with a total base value (TBN) of about 250 or less, and a second with a lower TBN than the aforementioned components. A low ash gas engine oil containing a small amount of additive mixture containing a mixture of detergents containing alkali or alkaline earth metal salts. The TBN of this alkaline or alkaline earth metal salt will typically be less than about half that of the aforementioned components.

0007Patent Document 3 provides a lubricating oil for a natural gas engine containing a major amount of lubricating viscosity base oil and a small mixture of one or more metal salicylate cleaners and one or more metal phenolates and / or metal sulfonate cleaners. Regarding the composition.

0008The lubricating base oil is any natural or synthetic lubricating base oil base oil distillate typically having a kinematic viscosity at 100 ° C of about 5-20 cSt, more preferably about 7-16 cSt, most preferably about 9-13 cSt. Minutes. In a preferred embodiment, the use of a viscosity index improver allows the elimination of oils with a viscosity of about 20 cSt or higher at 100 ° C. from the lubricating oil base oil fraction used to make the formulations of the present invention. Therefore, preferred base oils, if any, contain a small amount of heavy fractions; for example, a small amount of a lubricating oil fraction with a viscosity of 20 cSt or more at 100 ° C.

0009The lubricating oil base oil can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable lubricating base oils include not only hydrocracked base oils produced by hydrocracking the aromatic and polar components of crude oils (rather than solvent extraction), but also synthetic and slack waxes. Examples include base oils obtained by isomerization. Suitable base oils include those of API categories I, II and III, where the saturation level and viscosity index are: Group I-less than 90% and 80-120, respectively; Group II-> 90% and 80-120; and respectively Group III-Over 90% and Over 120, respectively Is.

0010The detergent mixture is used in combination with other metal salts or groups of metal salts (listed below) in an amount sufficient to achieve a lubricating oil of at least 0.65 wt% sulfate ash, approximately 150 A group of first metal salts or metal salts selected from the group consisting of one or more metal sulfonates, salicylates, phenolates and mixtures thereof, having a high TBN of more than ultra-300, preferably about 160-300, about 50. A group of secondary metal salts or metal salts selected from the group consisting of one or more metal salicylates, metal sulfonates, metal phenolates and mixtures thereof having a TBN of ultra-150, preferably about 60-120, and as well. A tertiary metal salt selected from the group consisting of one or more metal sulfonates identified as neutral or low TBN, metal salicylates and mixtures thereof, having a TBN of about 10-50, preferably about 20-40 or The total amount of medium plus neutral / low TBN detergent, including the group of metal salts, is about 0.7% by volume or more (active ingredient), preferably about 0.9% by volume or more (active ingredient), most preferably about 1% by volume or more. (Active ingredient), where at least one of the medium or low / neutral TBN detergents is metal salicylate, preferably at least one of the medium TBN detergents is metal salicylate. The total amount of the high TBN detergent is about 0.3% by volume or more (active ingredient), preferably about 0.4% by volume or more (active ingredient), and most preferably about 0.5% by volume (active ingredient). The mixture contains at least two different types of salts, with neutral or neutral salicylate as an essential ingredient. The volume ratio (based on the active ingredient) of the high TBN detergent to medium plus neutral / low TBN detergent is in the range of about 0.15 to 3.5, preferably 0.2 to 2, and most preferably about 0.25 to 1.

0011The amount of the cleaning agent mixture is about 10% by volume or less based on the active ingredient in the cleaning agent mixture, preferably about 8% by volume or less based on the active ingredient, and more preferably based on the active ingredient in the cleaning agent mixture. It is added to the lubricating oil formulation in an amount of about 1.5 to 5.0% by volume or less, most preferably about 1.5 to 5.0% by volume based on the active ingredient in the detergent mixture. Preferably, the total amount of metal salicylate used in all TBNs is in the range of 0.5% to 4.5% by volume based on the active ingredient of the metal salicylate.

0012Patent Document 4 describes about 40 cSt (mm) at 100 ° C.²PAO with a viscosity of (/ sec) and about 2.0 cSt (mm) at 100 ° C²Lubricants useful for the preparation of finished automotive gear lubricants and gear oils, including blends with esters having a viscosity of less than or equal to PAO and blends of PAO with esters having a viscosity index greater than or equal to the PAO viscosity index With respect to compositions, automotive gear lubricating compositions and fluids. This composition comprises thickeners, antioxidants, inhibitors packages, rust preventives, dispersants, cleaners, friction improvers, traction improvers, emulsification breakers, defoamers, dyes and anti-fog agents. May be further contained.

0013Patent Document 5 relates to a detergent additive for a lubricating oil composition containing at least two low, medium and high TBN detergents, preferably calcium salicylate. The cleaning agent is present in a lubricating oil composition comprising one of a Group II base oil, a Group III base oil or a wax isomer base oil and a mixture thereof, and a small amount of an optional co-base oil. Co-base oils include low and medium and high viscosity oils of polyalphaolefin oligomers, dibasic acid esters, polyol esters, other hydrocarbon oils, supplemental hydrocarbyl aromatic compounds and the like.

0014Patent Document 6 states that the lubricating oil is 96 (mm) at 100 ° C.²/ Sec) For lubricating oil blends for improved micro-pitching properties, including at least two base oils with a viscosity difference between the first and second base oils above. At least one base oil is 6mm²Less than / sec but 2mm²It is a polyalphaolefin with a viscosity of over / sec, and the second base oil is 100 mm at 100 ° C.²Over / sec but 300mm²Synthetic oil with a viscosity of less than / sec. The second base oil can be a high viscosity polyalphaolefin.

0015Patent Document 7 describes 96 cSt (mm) at 100 ° C.²For lubricating oil blends containing at least two base oils with a viscosity difference between the first and second base oils above (/ sec), the lubricating oils show improved exhaust. This blend is 10 cSt (mm) at 100 ° C²Less than / sec) but 2cSt (mm²100 cSt (mm) at 100 ° C with at least one synthetic PAO with a viscosity greater than / sec.²/ Sec) Super but 300cSt (mm²Contains a second synthetic oil with a viscosity of less than / sec). Lubricants may contain anti-wear agents, antioxidants, defoamers, emulsifying breakers, cleaning agents, dispersants, metal passivators, friction reducing agents, rust inhibitors and mixtures thereof. it can.

0016Patent Document 8 is a lubricating oil containing at least two base oils, in which the first base oil is 40 cSt (mm) at 100 ° C.²Molecular weight distribution (MWD) as a function of viscosity over viscosity and at least less than 10% algorithm: MWD = 0.2223 + 1.0232 * log (Kv at 100 ° C in cSt units) The second base oil is 10cSt (mm) at 100 ° C.²For lubricating oils with viscosities less than / sec). Preferably, the difference in viscosity between the first base oil and the second base oil is 30 cSt (mm) at 100 ° C.²/ Sec) is over. Preferably, the first base oil is a metallocene-catalyzed PAO base oil. The second base oil should be selected from GTL lubricants, wax-derived lubricants, PAOs, brightstocks, brightstocks with PIB, group I base oils, group II base oils, group II base oils and mixtures thereof. Can be done. The lubricating oil can contain additives, including detergents. Preferably the first base oil is 300 cSt (mm) at 100 ° C.²/ Sec) Super viscous, second base oil is 1.5 cSt mm at 100 ° C²/ Sec ~ 6cSt (mm²It has a viscosity of (/ sec). Preferably, the difference in viscosity between the first base oil and the second base oil is 96 cSt (mm) at 100 ° C.²/ Sec) is over.

0017Patent Document 9 is a lubricating oil containing at least two base oils, wherein the first base oil is at least 300 cSt (mm) at 100 ° C.²Viscosity (/ sec) and molecular weight distribution (MWD) as a function of viscosity with an algorithm of at least less than 10%: MWD = 0.2223 + 1.0232 * log (KV at 100 ° C in cSt units) The second base oil is 100 ° C and 100cSt (mm)²For lubricating oils with viscosities less than / sec). Preferably, the difference in viscosity between the first base oil and the second base oil is 250 cSt (mm) at 100 ° C.²/ Sec) is over. Preferably, the first base oil is a metallocene-catalyzed PAO base oil. The second base oil is GTL base oil, wax-derived base oil, PAO, bright stock, bright stock with PIB, group I base oil, group II base oil, group III base oil, group V base oil, group VI. You can choose from base oils and mixtures thereof. The lubricating oil can contain additives, including detergents.

0018Patent Document 10 relates to a long-life gas engine lubricating oil containing a cleaning agent. This lubricating oil contains a major amount of base oil with a lubricating viscosity and a small amount of a mixture of one or more metal sulfonates and / or phenolates and one or more metal salicylate cleaning agents, all of which are the same in the mixture. Or have substantially the same total base titer (TBN).

0019Lubricating oil Base oil is about 5 ~ 20cSt (mm)²/ Sec), more preferably about 7 ~ 16cSt (mm)²/ Sec), most preferably about 9 ~ 13cSt (mm)²/ Second) Any natural or synthetic lubricating base oil fraction that typically has kinematic viscosities at 100 ° C. In a preferred embodiment, the use of a viscosity index improver has a viscosity of 20 cSt (mm) at 100 ° C from the lubricating oil base oil fraction used to make the formulations of the present invention.²/ Sec) Allows the elimination of more than oil. Therefore, the preferred base oil, if any, is a small amount of heavy fraction; for example, a small amount of 100 ° C and a viscosity of 20 cSt (mm).²It contains a lubricating oil fraction of (/ sec) or more.

0020The lubricating oil base oil can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable lubricating oil base oils are produced by hydrocracking (rather than solvent extraction) the base oils obtained by isomerization of synthetic and slack waxes, as well as the aromatic and polar components of the crude oil. Hydrogenated decomposition product base oil can be mentioned. Suitable base oils include those of API categories I, II and III, where the saturation level and viscosity index are: Group I-less than 90% and 80-120, respectively; Group II-> 90% and 80-120; and respectively Group III-Over 90% and Over 120, respectively Is.

0021The detergent is a mixture of one or more metal sulfonates and / or metal phenolates and one or more metal salicylates. The metal is any alkali or alkaline earth metal; for example, calcium, barium, sodium, lithium, potassium, magnesium, more preferably calcium, barium and magnesium. It is a feature of the lubricating oils of the present invention that each of the metal salts used in the mixture has the same or substantially the same TBN as the other metal salts in the mixture; therefore, this mixture is one or more metals. One or more metal sulfonates combined with one or more metal salicylates, each of which is a low TBN detergent, or each of which is a medium TBN detergent, or each of which is a high TBN detergent, and / Alternatively, a metal phenolate can be included. Preferably each is a low TBN cleaning agent, and each metal cleaning agent has the same or substantially the same similar TBN below about 100. For the purposes of this specification and the accompanying claims, for metal salts, low TBN means less than 100 TBN; medium TBN means less than 100-250 TBN; and high TBN means about 250. It means the above TBN. The same or substantially similar TBN means that salt TBNs never fall within the same TBN category, but are absolutely close to each other, even within a given TBN category; for example, low, medium and high. To do. Therefore, a mixture of sulfonate and / or phenolate and low TBN salicylate is not only composed of less than 100 TBN salts, but each salt is paired with other salts in the mixture; for example, TBN64 salicylate. It will have substantially the same TBN as that of the TBN60 sulfonate, or the TBN65 phenolate paired with the TBN64 salicylate. Therefore, individual salts will not have TBNs that are at the opposite end of the applicable TBN category or that are substantially different from each other.

0022The TBN of the salt will differ by about 15% or less, preferably about 12% or less, more preferably about 10% or less.

0023One or more metal sulfonates and / or metal phenolates, as well as one or more metal salicylates, are, for example, 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably 20:80 to 80. Used as a cleaning agent as a mixture in a weight ratio of: 20.

0024The amount of the cleaning agent mixture is about 10% by volume or less based on the active ingredient in the cleaning agent mixture, preferably about 8% by volume or less based on the active ingredient, and more preferably based on the active ingredient in the cleaning agent mixture. It is added to the lubricating oil formulation in an amount of about 0.3% by volume to 3% by volume based on the active ingredient in the detergent mixture, not more than about 6% by volume.

0025Patent Document 11 is a lubricating oil for a two-stroke crosshead marine diesel engine containing a base oil and an oil-soluble hyperbasic detergent additive in the form of a complex, which contains two basic detergents. The present invention relates to a lubricating oil stabilized by the above surfactant. Two or more surfactants are (1) sulfurized and / or non-sulfided phenol and one other surfactant that is not a phenolic surfactant; (2) sulfurized and / or non-sulfated salicylic acid and salicylic acid-based surfactants. Not one other surfactant; or (3) at least three surfactants that are sulfided or non-sulfided phenol, sulfided or non-sulfurized salicylic acid and one other surfactant that is not phenolic or salicylic acid-based surfactant. Or (4) a mixture of at least three surfactants, sulfided or non-sulfided phenol, sulfided or non-sulfided salicylic acid, and at least one sulfate surfactant.

0026The base oil is an oil having a lubricating viscosity and may be any oil suitable for system lubrication of a crosshead engine. The lubricating oil may preferably be animal, plant or mineral oil. Preferably, the lubricant is a petroleum-derived lubricant, such as a naphthenic-based, paraffin-based or mixed-based oil. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthetic lubricants include synthetic ester lubricants, including diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricants such as liquid polyisobutylene and polyalphaolefins. Can be mentioned. Generally, mineral oil is used. Lubricating oil generally accounts for more than 60% by weight, typically more than 70% by weight, of the lubricating oil composition, typically 2-40 mm.²/ Sec, for example 3 ~ 15mm²It has kinematic viscosity at 100 ° C / sec and a viscosity index of 80-100, for example 90-95.

0027Another class of lubricating oil is a hydrocracked oil in which the refining process further decomposes intermediate and heavy distillate fractions at high temperature and medium pressure in the presence of hydrogen. Hydrocracked oil is typically 2-40, for example 3-15 mm²It has kinematic viscosities at 100 ° C / sec and typically has a viscosity index in the range of 100-110, for example 105-108.

0028Bright stock is 28 ~ 36mm²Less than 30% by weight, preferably less than 20, more preferably less than 30% by weight, based on the mass of the lubricating oil composition, solvent-extracted and demolded from vacuum residual oil, which generally has a kinematic viscosity at 100 ° C./sec. Means the base oil typically used in proportions of less than 10% by weight, such as less than 15, most preferably less than 5% by weight.

0029Patent Document 12 describes an oil having a lubricating viscosity, a TBN of a dispersant in the range of 70 to 45, and a cleaning agent containing at least one calcium salicylate having 0 to 0.2% by mass of nitrogen based on the mass of the oil composition. And with respect to detergent gas fuel engine lubricants containing small amounts of one or more co-additives. The base oil can be any animal, plant or mineral oil or synthetic oil. Base oil is used in proportions of more than 60% by weight of the composition. This oil is typically 2-40, for example 3-15 mm²It has a viscosity at 100 ° C / sec and a viscosity index of 80-100. 2 ~ 40mm at 100 ° C²Hydrocracked oils with a viscosity of / sec and a viscosity index of 100-110 can also be used. 28 ~ 36mm²Brightstock with a viscosity at 100 ° C./sec can also be used in a proportion of typically less than 30% by weight, preferably less than 20, and most preferably less than 5% by weight.

0030Patent Document 13 has a boron content of more than 95 ppm, including a viscosity index of 80-120, at least 90% by weight saturated, 0.03% by weight or less of sulfur and a major amount of lubricating oil with at least one cleaning agent. Regarding gas engine oil. Metal salicylate is the preferred cleaning agent.

0031Patent Document 14 describes high-viscosity synthetic hydrocarbons such as high-viscosity PAO, liquid hydrogenated polyisoprene, or 40 to 1000 cSt (mm) at 100 ° C.²Ethylene-alpha olefin copolymer with viscosity (/ sec), 1-10 cSt (mm) at 100 ° C²Low-viscosity synthetic hydrocarbons with a viscosity of (/ sec), optionally 1-10 cSt (mm) at 100 ° C²For low viscosity esters with a viscosity of (/ sec), and optionally a lubricating oil composition containing 25% by weight or less of an additive package.

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<p num="0033"> The present invention is a fuel economy for large low speed, medium and high speed engines lubricated with lubricating oils, where the interface (or contact surface) speed reaches at least about 3 mm / sec, preferably at least about 10 mm / sec. It is directed to a method of improving the properties by lubricating the engine and reducing the traction coefficient of the engine oil. This is 13 ~ 30mm at 100 ° C²/ Sec, preferably 16-30 mm²/ Sec, more preferably 18-25 mm²/ Sec, most preferably 20-25 mm²It has a kinematic viscosity of / sec and a base titer (BN) of at least 5 mg KOH / g, preferably 40-100 mg KOH / g, more preferably 40-70 mg KOH / g. Two different base oils, 2 ~ 16mm at 100 ° C²/ Sec, preferably 2-12 mm²One or more oils selected from the group consisting of Group II base oils, Group III base oils and Group IV base oils, preferably Group III and Group IV base oils, more preferably Group III base oils, having kinematic viscosities of / sec. At least 38 mm with 1 base oil and 100 ° C²/ Sec, preferably 38-1200 mm²/ Sec, more preferably 38-600 mm²/ Sec, even more preferably 38-300 mm²Less than / sec, most preferably 38-150 mm²Second base oil selected from one or more oils selected from Group IV base oils with kinematic viscosities of / sec Base oil containing a bimodal blend with, as well as Alkaline and / or alkaline earth at all treatment levels (based on the active ingredient) from 6% by weight to 40% by weight, preferably 8-40% by weight, more preferably 10-30% by weight. Metals, preferably alkaline earth metals, more preferably calcium salicylates, phenolates, carboxylates, sulfonates, mixtures of salicylates and phenolates or mixtures of phenolates and carboxylates, preferably phenolates, salicylates and carboxys. A detergent selected from a rate or a mixture of phenolate and carboxylate or a mixture of phenolate and salicylate. Achieved by using a lubricating oil containing, as an engine oil, Here, the improvement in fuel economy is not bimodal or is based solely on Group I and / or Group II base oils or at least 38 mm at 100 ° C.²The traction factor of the engine oil with its bimodal blend is higher than the traction factor of the engine oil containing no Group IV base oil with KV / sec or containing a different detergent or detergent mixture. Proven by being low.</p><p num="0034"> "Surface speed" means the speed at which interface surfaces in an engine, such as cylinder walls and pistons, or bearing interface surfaces, pass each other as the engine operates. This surface velocity is a major factor influencing whether the lubrication regime for interface surfaces is boundary, hydrodynamic or mixed (boundary / hydrodynamic).</p><p num="0035"> For engines that reach a surface speed of at least about 30 mm / sec, preferably at least 60 mm / sec, more preferably at least 75 mm / sec, most preferably at least 100 mm / sec, the first base oil is 2-16 mm at 100 ° C.²/ Sec, preferably 2-12 mm²One or more of Group II, Group III and Group IV base oils, preferably Group III and Group IV base oils with kinematic viscosities of / sec, and the second base oil is at least 38 mm.²/ Sec, preferably 38-1200 mm²/ Sec, more preferably 38-600 mm²/ Sec, even more preferably 38-300 mm²One or more of Group IV base oils with kinematic viscosity of / sec, the detergent is any alkaline and / or alkaline earth metal, preferably alkaline earth metal, more preferably calcium, salicylate, phenolate, sulfonate, It can be carboxylate and mixtures thereof, and the total amount of detergent used is more than 6% by weight of the lubricating oil (based on the active ingredient) to 40% by weight, preferably 8-40% by weight. , More preferably in the range of 10-30% by weight, most preferably 12-25% by weight, and the lubricating oil is at least 5 mg KOH / g, preferably 40-100 mg KOH / g, more preferably 40-70 mg KOH /. TBN of g and 6 ~ 30mm at 100 ° C²/ Sec, preferably 8-25 mm²/ Sec, more preferably 12-20 mm²Has kinematic viscosity of / sec.</p><p num="0036"> In another embodiment for engines that reach a surface speed of at least 3 mm / sec, the first base oil is 2-16 mm at 100 ° C.²/ Sec, preferably 2-12 mm²One or more Group II, Group III and Group IV base oils, preferably Group III and Group IV base oils with a KV of / sec, the second base oil is 38 mm at 100 ° C.²/ Sec to 300 mm²Less than / sec, preferably 38-150 mm²One or more Group IV base oils with KV (or kinematic viscosity) of / second, where the cleaning agent is alkaline and / or alkaline earth metal, preferably alkaline earth metal, more preferably calcium, sulfonate cleaning agent or Alkaline and / or alkaline earth metals, preferably alkaline earth metals, more preferably calcium, a mixture of phenolates and sulfonate, the total amount of detergent is 6% by weight of the lubricating oil (based on the active ingredient). In the range of more than 40% by weight, preferably 8 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 12 to 25% by weight, where phenolate is the total amount of lubricating oil. Alkaline is present in an amount in the range of 5-30% by weight, preferably 8-30% by weight, more preferably 10-30% by weight, with the sulfonate being 1-10% by weight, preferably 2-10% by weight. %, More preferably in an amount in the range of 3-10% by weight, the lubricating oil is at least 5 mg KOH / g, preferably 40-100 mg KOH / g, more preferably 40-70 mg KOH / g BN, and. 13 ~ 30mm at 100 ° C²/ Sec, preferably 16-30 mm²/ Sec, more preferably 18-25 mm²Has kinematic viscosity of / sec.</p><p num="0037"> In another embodiment the invention The difference in kinematic viscosity between the 1st base oil and the 2nd base oil is at least 30mm²/ Sec, 2 ~ 16mm at 100 ° C²First base oil selected from the group consisting of Group II base oil, Group III base oil and Group IV base oil with kinematic viscosity of / sec, and at least 38 mm at 100 ° C.²With a second base oil selected from Group IV base oils with kinematic viscosities of / sec, as well as Alkaline and / or alkaline earth metal salicylate, phenolate, carboxylate, sulfonate, pheno at all treatment levels in amounts from 6% to 40% by weight (active ingredient) based on the total weight of the lubricating oil. A lubricant selected from a mixture of rate and salicylate or a mixture of phenolate and carboxylate. Including, 6 ~ 30mm at 100 ° C²/ Sec, preferably 13-30 mm²By using a lubricating oil with a kinematic viscosity of / sec and a base value of at least 5 mg KOH / g as the engine oil, the traction coefficient of the engine oil used to lubricate the engine is reduced. A method of improving the fuel economy of large low speed, medium and high speed engines, lubricated by, reaching a surface speed of at least about 3 mm / sec, preferably at least about 30 mm / sec. Improved fuel economy includes a single base oil component of Group II base oil, Group III base oil or Group IV base oil, or 30 mm²Contains an equivalent (or equivalent) base oil blend with a difference in kinematic viscosity between the first and second base oils less than / sec or based solely on Group I and / or Group II base oils or at 100 ° C. At least 38mm²Towards a method that is proven by having a lower traction factor for an engine oil with the same kinematic viscosity at 100 ° C, which does not contain any Group IV base oil with a kinematic viscosity of / second. There is.</p>

0038<figref num="1">Group III (6.5mm²/ Sec) Base oil and Group IV base oil (PAO 150) and Group III (6.5 mm)²/ Sec) Base oil and Group IV base oil (PAO 300) based formulations (or formulations), all utilizing the same detergent package containing a mixture of phenolate and sulfonate, all formulations Contains a detergent having a formulation BN of 70, and the blend shows the effect on traction coefficient vs. velocity (mm / sec) of the formulation which differs in terms of kinematic viscosity relative to control oil A.</figref><figref num="2">20mm at 100 ° C, using different cleaning agents²Group III (6.5 mm) blended with KV (or kinematic viscosity) of / sec²/ Sec) Effect on traction coefficient vs. velocity (mm / sec) of oil formulations based on base oils and Group IV base oils (PAO 150) and containing detergents with a formulation BN of 70 , Control oil B (Ref. B), which is a blend containing only a mixture of control oil A (Ref. A) and base oil.</figref><figref num="3A">Group III (6.5 mm) blended with different kinematic viscosities utilizing a mixture of phenolate and salicylate cleaners²/ Sec) Traction coefficient for formulations based on base oils and two different Group IV base oils (PAO 150 and PAO 300), all formulations containing a detergent with a formulation BN of 70. The effect on velocity (mm / sec) is shown for control oil A (Ref. A).</figref><figref num="3B">Group III (6.5 mm) blended to different blend kinematic viscosities and utilizes a mixture of phenolate and salicylate detergents (blended to 40 and 70 different formulation base values).²Control oil A (Ref. A) (Phenolate) on the effect of formulations based on the base oil and two different Group IV base oils (PAO 40 and PAO 150) on the traction factor vs. velocity (mm / sec). / Contains sulfonate detergent) and Group III (6.5mm)²/ Sec) Shown for control oil B (Ref. B), which is a blend of base oil and Group IV (PAO 150) base oil only.</figref><figref num="4">Formulations based on blends of Group I base oils with different kinematic viscosities and blends with different blend kinematic viscosities, utilizing a mixture of phenolate and salicylate cleaners, and with phenolate and salicylate cleaners. A formulation based on a blend of Group IV base oils (PAO 8 and PAO 40) of different kinematic viscosities containing a mixture of, traction coefficient vs. velocity of a formulation containing a detergent with a formulation BN of 70. Effect on (mm / sec), control oil A (Ref. A) and group III (6.5 mm)²/ Sec) Shown for control oil B (Ref. B), which is a blend of base oil and Group IV (PAO 150) base oil only.</figref><figref num="5">Group I (12 mm) containing a mixture of phenolate and salicylate cleaners²/ Seconds) Different kinematics mixed with Group IV (PAO 40 and PAO 150) base oils containing base oils and Group IV base oil (PAO 150) based formulations and mixtures of phenolate and salicylate cleaners. Viscosity Group II (3mm)²/ Sec and 12mm²Control oil A, which is a base oil-based formulation and all formulations contain a detergent with a formulation BN of 70 on the traction coefficient vs. velocity (mm / sec). (Ref.A) and Group III (6.5mm)²/ Sec) Shown for control oil B (Ref. B), which is a blend of base oil and Group IV (PAO 150) base oil only.</figref><figref num="6A">Utilizing different detergents, phenolate / salicylate or mixture of phenolate / sulfonate, 20 mm²Group III (6.5 mm) blended into blend KV at 100 ° C / sec²Traction factor vs. velocity (mm / s) of formulations based on base oils and Group IV (PAO 150) base oils, all formulations containing a detergent with a formulation BN of 70 The effect on control oil A (Ref. A) is shown.</figref><figref num="6B">Group III (6.5 mm) with a mixture of either phenolate and carboxylate cleaners or phenolate and salicylate cleaners²Effect on traction coefficient vs. velocity (mm / s) of two formulations based on (/ sec) base oil and Group IV (PAO 150) base oil, containing a detergent with a formulation BN of 70 The control oil A (Ref. A) and Group III (6.5 mm)²/ Sec) Shown for control oil B (Ref. B), which is a mixture of base oil and Group IV (PAO 150) base oil only.</figref><figref num="7">20 mm at 100 ° C, utilizing a mixture of phenolate cleaner alone or salicylate cleaner alone or a mixture of salicylate cleaner and phenolate cleaner in different proportions or a mixture of phenolate, sulfonate and salicylate cleaner.²Group III (6.5mm) blended with / sec blend KV²The effect on traction coefficient vs. velocity (mm / s) of formulations based on base oils and Group IV base oils (PAO 150), all formulations having a formulation BN of 70. Shown for control oil A (Ref. A).</figref><figref num="8">Utilize a phenolic cleaning agent only, a salicylate cleaning agent alone or a mixture of a phenolate cleaning agent and a salicylate cleaning agent in different ratios, 20 mm at 100 ° C.²Group III (6.5mm) blended with / sec blend KV²The effect on traction coefficient vs. velocity (mm / s) of formulations based on base oils and Group IV base oils (PAO 150), all formulations having a formulation BN of 70. Shown for control oil A (Ref. A).</figref><figref num="9">Everything is 20mm at 100 ° C²Group III (6.5 mm) with either a phenolate cleaner alone or a mixture of a phenolate cleaner and a sulfonate cleaner blended into KV and 70 BN at / sec.²The effect of the base oil and Group IV base oil (PAO 150) based formulations on traction coefficient vs. velocity (mm / sec) is shown for control oil A (Ref. A).</figref>

0039The method of the present invention utilizes a bimodal mixture of base oils. Bimodal as used herein is a mixture of at least two base oils, each having a different kinematic viscosity at 100 ° C, at 100 ° C between at least two base oils in a bimodal blend. At least 30 mm difference in kinematic viscosity²Means a mixture that is / second. A mixture of at least two base oils is at least 38 mm²Combined with one or more high kinematic group IV base oils with KV at 100 ° C / sec, the base oil is selected from the group consisting of Group II, Group III and Group IV base oils using API classification. 2 ~ 16mm²/ Sec, preferably 2-12 mm²Contains one or more low kinematic viscosity base oils with kinematic viscosity at 100 ° C / sec.

0040As used herein and in the appended claims, the terms "base oil" and "base oil" are used interchangeably and interchangeably.

0041Group II base oils are classified by the American Petroleum Institute as oils containing 90% or more saturated products, 0.03% by weight or less sulfur and 80 or more and less than 120 viscosity indexes.

0042Group III base oils are classified by the American Petroleum Institute as oils containing 90% or more saturated products, 0.03% or less sulfur and a viscosity index of 120 or more. Group III base oils are usually very hydrocracked oil feedstocks, such as vacuum gas oils (or light oils), to remove impurities and saturate all possible aromatic compounds. A step of producing a high paraffin-based lubricating oil base oil having a high viscosity index, a step of subjecting a hydrocracked base oil to a selective catalytic hydrogen dewaxing treatment for converting normal paraffin into branched paraffin by isomerizing normal paraffin. It is manufactured using a three-step process that includes subsequent hydropurification to remove any residual aromatic compounds, sulfur, nitrogen or oxygenates.

0043Group III base oils are also (1) one or more gas liquefied (GTL) substances; and (2) hydride delowed or hydrogen derived from synthetic waxes, natural waxes or waxy feedstocks. An isomerized / contact (and / or solvent) dewaated base oil and / or base oil in which the waxy raw materials are gas oil (or light oil), slack wax (natural oil, mineral oil or synthetic oil, Mineral oils and / or non-mineral oils waxy feedstocks and waxy fuel hydrocracker bottoms, waxy raffinates, hydrocracked products, such as Fischer-Tropsch (derived from solvent dewaxing of feedstock). Waxous base oils such as thermal decomposition products, foot oils or other minerals, mineral oils, or waxy substances recovered from coal liquefied or shale oils, about 20 or more, preferably about 30 or more carbons. One of the base oils and / or base oils derived from base oils and / or base oils containing even non-petroleum-derived waxy substances such as a number of linear or branched hydrocarbyl compounds and mixtures of such base oils and / or base oils. Or include non-conventional or uncommon base oils and / or base oils containing mixtures.

0044GTL substances include gaseous carbon-containing compounds such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylene and butine, hydrogen-containing compounds and / or feedstock oils. A substance derived from one or more synthetic, binding, transforming, rearranged, and / or degrading / disruptive processes. GTL base oils and / or base oils are generally derived from hydrocarbons; for example, waxy synthetic hydrocarbons derived from themselves, simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or components as feedstocks. It is a GTL substance with a lubricating viscosity. As a GTL base oil and / or base oil, an oil that boils in the lubricating oil boiling range (1) A lubricating oil that has been separated / partitioned from synthetic GTL substances, such as by distillation, and then lowered / low flow point Was subjected to a final waxing step involving either or both a catalytic dewaxing process, or a solvent dewaxing process; (2), for example, hydrocarbon dewaxed or hydrogen isomerized. Synthetic wax isomers, including contact and / or solvent dewaxed synthetic waxes or waxy hydrocarbons; (3) Hydrodewaxed or hydrogen isomerized contacts and / or solvent dewaxed Treated Fischer-Tropsch (FT) substances (ie hydrocarbons, waxy hydrocarbons, waxes and possible similar oxygenates); preferably hydrodewaxed or hydrogen isomerized / continued contact and / or Solvent dewaxed dewaxed FT waxy hydrocarbons, or hydrodewaxed or hydrogen isomerized / subsequently contact (and / or solvent) dewaxed dewaxed FT waxes, or theirs Examples include mixtures.

0045GTL base oils and / or base oils derived from GTL substances, especially hydrogenated or hydrogenated / hydrogen isomerized / subsequently contacted and / or solvent dewaxed waxes or waxy raw materials, preferably FT substances. Derived base oil and / or base oil is about 2 mm at 100 ° C²/ Sec ~ about 50mm²It is typically characterized as having a kinematic viscosity of / sec (ASTM D445). They are typically further characterized as having a pour point (ASTM D97) of -5 ° C to about -40 ° C or less. They are also typically characterized as having a viscosity index (ASTM D2270) of about 80 to about 140 or higher.

0046In addition, GTL base oils and / or base oils are typically highly paraffinic (&gt; 90% saturated) and may contain a mixture of monocycloparaffin and multicycloparaffin in combination with acyclic isoparaffin. .. The ratio of naphthenic (ie, cycloparaffin) content in such combinations varies with the catalyst and temperature used. In addition, GTL base oils and / or base oils typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, more typically less than about 5 ppm of each of these elements. The sulfur and nitrogen content of GTL base oils and / or base oils obtained from FT substances, especially FT waxes, is essentially zero. In addition, the absence of phosphorus and aromatic compounds makes this material particularly suitable for the formulation of low SAP products.

0047The terms GTL base oil and / or base oil and / or wax isomer base oil and / or base oil are such substances in a wide viscosity range such that they are recovered in the manufacturing process to produce a blend that exhibits a target kinematic viscosity. , And understood to include each fraction of a mixture of two or more such fractions, and a mixture of one or more low viscosity fractions and one or more higher viscosity fractions. It should be.

0048The GTL material from which the GTL base oil and / or base oil is derived is preferably an FT material (ie, hydrocarbons, waxy hydrocarbons, waxes).

0049In a preferred embodiment, the GTL substance from which the GTL base oil and / or base oil is derived is an FT substance (ie, a hydrocarbon, a waxy hydrocarbon, a wax). Slurry FT synthesis process synthesizes raw materials from those using FT catalysts containing CO and hydrogen and, in particular, FT catalysts containing catalytic cobalt components to provide higher Schultz-Flory kinetic alpha for producing more desirable higher molecular weight paraffins. It may be conveniently used to do so. This process is also well known to those of skill in the art.

0050GTL base oil and / or base oil, hydrogenated or hydrogenated / contact (and / or solvent) dewaxed FT substance-derived base oil, and wax isomers or hydrogenated dewaxed A useful composition of a wax-derived hydrogenated or hydrogenated / contact (and / or solvent) dewaxed base oil, such as a treated product, is described, for example, in US Pat. No. 6,080,301. No. 6; No. 6,090,989, and No. 6,165,949.

0051Base oils and / or base oils derived from waxy feedstocks that are also suitable for use as Group III base oils in the present invention are mineral oils, non-mineral oils, non-oil oils, or natural sources such as gas oils, slacks. Raw oils such as waxes, waxy fuel hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hydrocracked products, thermal cracked products, foot oils, one or more waxes from coal liquefaction or shale oil, or Other suitable mineral oils, non-mineral oils, non-petroleum or naturally occurring waxy substances, linear or branched hydrocarbyl compounds having about 20 or more, preferably about 30 or more carbon atoms, and such isomers. Hydrocarbon dewaxed or hydrogen isomerized / contact (and / or solvent) dewaxed waxy feedstock derived from / iso-dewalated base oils and / or base oil mixtures It is a viscous paraffinic fluid.

0052Slack wax is a wax recovered from any waxy hydrocarbon oil, including synthetic oils such as FT waxy oils or petroleum, by solvent or automatic cooling dewaxing. The solvent dewaxing treatment uses a cooled solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), a mixture of MEK / MIBK, and a mixture of MEK and toluene, while the automatic cooling dewazing treatment uses propane or butane. Use pressurized liquefied low boiling hydrocarbons such as.

0053Slack waxes secured from synthetic waxy oils such as FT waxy oils will usually have zero or no sulfur and / or nitrogen-containing compound content. Slack wax secured from petroleum may contain sulfur and nitrogen-containing compounds. Such heteroatom compounds are hydrotreated (and), such as by hydrodesulfurization (HDS) and hydrodesulfurization (HDN), to avoid subsequent poisoning / inactivation of hydrogen isomerization catalysts. Must be removed by (not hydrocracking).

0054The process of producing a lubricating base oil from a waxy base oil, such as slack wax, FT wax or waxy feedstock, may be characterized as an isomerization process. When slack waxes are used as raw materials, they contain sulfur- and nitrogen-containing compounds (catalysts) that would otherwise inactivate the hydrogen isomerization or hydrogenation dewading catalyst used in the next step. May need to be subjected to a pre-hydrogenation process under conditions already well known to those of skill in the art to reduce or eliminate (to levels that would effectively avoid poisoning or inactivation). There is. When FT waxes are used, such reserves, as such waxes only have a trace amount of sulfur or nitrogen compound content (less than about 10 ppm, or more typically less than about 5 ppm to none). No processing is required. However, some hydrodewaxing catalysts fed with FT wax may benefit from prehydrogenation for the removal of oxygenate, while others may benefit from oxygenation. is there. The hydrogen isomerization or hydrogenation dewaxing process may be carried out on a combination of catalysts or on a single catalyst.

0055After any required hydrodesulfurization or hydrodesulfurization, the hydrogenation used for the production of base oils from such waxy raw materials is non-hydrogenation, such as lubricating oil hydrocracking (LHDC) catalysts. Hydrodesulfurization / hydrogen isomerization catalysts of crystals, such as catalysts containing oxide carriers such as alumina, silica, silica / alumina containing Co, Mo, Ni, W, Mo, etc., or hydrogenation of crystals. A decomposition / hydrogenation catalyst, preferably a zeolite-based catalyst, may be used.

0056Hydrocarbon conversion catalysts useful for the conversion of n-paraffin waxy feedstocks disclosed herein for forming isoparaffin-based hydrocarbon base oils are as disclosed in US Pat. No. 4,906,350. Zeolite catalysts such as ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, Offretite, ferrierite, zeolite beta, zeolite theta, and zeolite alpha. These catalysts are used in combination with Group VIII metals, especially palladium or platinum. Group VIII metals may be incorporated into the zeolite catalyst by conventional techniques such as ion exchange.

0057In one embodiment, the conversion of waxy feedstock is carried out on a combination of Pt / zeolite beta and Pt / ZSM-23 catalyst in the presence of hydrogen, or on such catalysts used continuously. You may be broken. In another embodiment, the process of producing a lubricating base oil comprises hydrogen isomerization and dewaxing on a single catalyst, such as Pt / ZSM-35. Moreover, in another embodiment, the waxy raw material is either a 1-stage or 2-stage, Group VIII metal-supported ZSM-48, preferably Group VIII noble metal-supported ZSM-48, more preferably Pt / ZSM-48. Can be supplied on a catalyst containing. In all cases, useful hydrocarbon-based oil products can be obtained. The catalyst ZSM-48 is described in US Pat. No. 5,075,269.

0058The dewaxing process may be accomplished, when required, using one or more of solvent dewaxing, catalytic dewaxing or hydrodewaxing processes or a combination of such processes in any order. ..

0059In solvent dewaxing, the hydrogen isomer is contacted with a cooled solvent such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ME / MIBK mixture, or MEK / toluene mixture, and In addition, the higher flow point material is further cooled to precipitate as a waxy solid, which is then separated from the solvent-containing lubricating oil distillate that is raffinate. Raffinate is typically further cooled in a scraper surface cooler to remove more wax solids. At least a portion of it is flushed to cool the hydrogen isomer and precipitate the wax, for example automatic cooling using a low molecular weight hydrocarbon such as propane, which is a mixture of liquid propane and the hydrogen isomer. Dewaxing treatment can also be used. The wax is separated from the raffinate by filtration, membrane separation or centrifugation. The solvent is then stripped from the raffinate and the raffinate is then fractionated to produce the preferred base oil useful in the present invention.

0060In the catalytic dewaxing process, the hydrogen isomer is reacted with hydrogen in the presence of a suitable dewaxing catalyst under conditions effective for lowering the pour point of the hydrogen isomer. The catalytic dewaxing process also converts some of the hydrogen isomers to lower boiling point materials, which are separated from the heavier base oil distillates. This base oil fraction can then be fractionated into two or more base oils. Separation of the lower boiling point material may be accomplished either before or during the fractional distillation of the heavy base oil fractionated material in the desired base oil.

0061Any dewaxing catalyst that will lower the pour point of the hydrogen isomer, and preferably one that provides a high yield of lubricating oil base oil from the hydrogen isomer, may be used. These include shape-selective molecular sieves that have proven useful for dewaxing petroleum fractions when combined with at least one catalytic metal component, such as ferrierite, mordenite, etc. Included are ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22, also known as Thetawan or RON, and Silicone aluminum phosphate known as SAPO. Surprisingly, the dewaxing catalysts found to be particularly effective include noble metals, preferably Pt, in combination with H-mordenite. The dewaxing process may be accomplished with a catalyst on a fixed bed, fluidized bed or slurry bed. Typical dewaxing conditions are temperatures in the range of about 400-600 ° F, pressures of 500-900 psig, and H of 1500-3500 SCF / B for flow-through reactors.₂Treatment ratios and LHSVs of 0.1 to 10, preferably 0.2 to 2.0 can be mentioned. The dewaxing process typically converts 40% by weight or less, preferably 30% by weight or less of the hydrogen isomer having an initial boiling point in the range of 650 to 750 ° F into a substance that boils below that initial boiling point. Is done for.

0062The primary base oil of the bimodal mixture can also be a Group IV base oil identified as a polyalphaolefin for the purposes of this specification and the appended claims.

0063Polyalphaolefins (PAOs) typically consist of relatively low molecular weight hydrogenated polymers or oligomers of polyalphaolefins, C.₂~ About C₃₂C containing alpha olefins such as 1-octene, 1-decene, 1-dodecene₈~ About C₁₆Alpha olefins are preferred, but not limited to them. Preferred polyalphaolefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and polyolefins derived from mixed olefins.

0064The PAO fluid comprises, for example, a complex of aluminum trichloride, boron trifluoride or boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate Friedel- It may be conveniently produced by polymerization of alpha olefins in the presence of a polymerization catalyst such as a Crafts catalyst. For example, the methods disclosed by US Pat. No. 4,149,178 or US Pat. No. 3,382,291 may be conveniently used herein. Other descriptions of PAO synthesis include the following U.S. Pat. Nos. It is found in Specification 4,434,408, Specification 4,910,355, Specification 4,956,122, and Specification 5,068,487. C₁₄~ C₁₈The olefin dimer is described in US Pat. No. 4,218,330.

0065PAOs useful in the present invention can also be produced by metallocene catalysis. The metallocene-catalyzed PAO (mPAO) can be a copolymer made from at least two alpha olefins or more in a metallocene catalytic system, or a homopolymer made from a single alpha olefin feedstock.

0066Metallocene catalysts are activated or promoted by non-coordinating anions, such as methylaluminoxane (MAO) or N, N-dimethylanilinium tetrakis (perfluorophenyl) borate or other equivalent non-coordinating anions. It can be a simple metallocene, a substituted metallocene or a crosslinked metallocene catalyst. Methods for producing mPAO using mPAO and metallocene catalysis are described in WO 2009/123800, Pamphlet 2007/011832, and US Patent Application Publication No. 2009/0036725.

0067Copolymer mPAO composition is C₃~ C₃₀Made from at least two alpha olefins in the range, the monomers are randomly distributed in the polymer. The average carbon number is preferably at least 4.1. Advantageously, ethylene and propylene, when present in the feedstock, are present individually in an amount of less than 50% by weight, or preferably less than 50% by weight in total. The copolymers of the invention can be isotactic, atactic, syndiotactic polymers or any other form of suitable stereoregularity.

0068mPAO is also C₃~ C₃₀It can be prepared from a mixed raw material linear alpha olefin (LAO) containing at least two selected from linear alpha olefins and up to 26 different linear alpha olefins. In a preferred embodiment, the mixed feed LAO is obtained from an ethylene growth treatment using an aluminum catalyst or a metallocene catalyst. Growth olefins are mostly C₆~ C₁₈Including LAO. LAO from other processes can also be used.

0069The homopolymer mPAO composition is C₃~ C₃₀Range, preferably C₃~ C₁₆, Most preferably C₃~ C₁₄Or C₃~ C₁₂Manufactured from a single alpha olefin selected from. Homopolymers can be isotactic, atactic, syndiotactic polymers or any other form of suitable stereoregularity. In many cases the stereoregularity can be carefully adjusted by the selected polymerization catalyst and polymerization reaction conditions or by the selected hydrogenation conditions.

0070Alpha olefins can be selected from any component from a regular LAO manufacturing facility or from a refinery. It was manufactured alone to produce homopolymers, or with another LAO available from refineries or chemical plants, including propylene, 1-butene, 1-pentene, etc., or from a dedicated manufacturing facility1 -Can be used with hexene or 1-octene. In another embodiment, the alpha olefin can be selected from alpha olefins made from Fischer-Tropsch synthesis (as reported in US Pat. No. 5,382,739). For example, C₃~ C₁₆Alpha olefins, more preferably linear alpha olefins, are suitable for producing homopolymers. C₄-And C₁₄-LAO, C₆-And C₁₆-LAO, C₈-, C₁₀-, C₁₂-LAO, or C₈-And C₁₄-LAO, C₆-, C₁₀-, C₁₄-LAO, C₄-And C₁₂-Other combinations, such as LAO, are suitable for making copolymers.

0071C₃~ C₃₀A mixture of LAO selected from LAO or C₃~ C₁₆Raw materials containing a single LAO selected from LAOs are contacted with activated metallocene catalysts under oligomerization conditions to provide a liquid product suitable for use in lubricating oil components or as functional fluids. .. The present invention is also C₃~ C₃₀Concerning copolymer compositions made from at least two alpha olefins in the range, and in which the monomers are randomly distributed in the polymer. The phrase "at least two alpha olefins" will be understood to mean "at least two different alpha olefins" (and similarly "at least three alpha olefins" means "at least three different alpha olefins" and so on. To do).

0072The product obtained is an essentially random liquid copolymer containing at least two alpha olefins. By "essentially random" is meant that one of ordinary skill in the art would consider the product to be a random copolymer. Similarly, the term "liquid" will be understood by those skilled in the art to mean a liquid under normal conditions of temperature and pressure, such as ambient temperature and pressure.

0073The process involves catalytic systems containing metallocene compounds (formula 1, below) along with activators such as non-coordinating anions (NCA) (formula 2, below) or methylaluminoxane (MAO) 1111 (formula 3, below). Is used.<chemistry num="1"><img id="000002" he="148" wi="120" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0074The term "catalytic system" is defined herein to mean a catalytic precursor / activator pair, such as a metallocene / activator pair. When a "catalytic system" is used to describe such a pair prior to activation, it is active with an activator and optionally a co-activator (such as a trialkylaluminum compound). It means an unmodified catalyst (pre-catalyst). When it is used to describe such a pair after activation, it means an activation catalyst and activator or other charge balance moiety. In addition, this activation "catalytic system" may optionally include a coactivator and / or other charge balancing moiety. Co-activators, such as optionally and often trialkylaluminum compounds, are also used as impurity scavengers.

0075Metallocenes are selected from one or more compounds according to Formula 1 above. In Equation 1, M is selected from Group 4 transition metals, preferably zirconium (Zr), hafnium (Hf) and titanium (Ti), with L1 and L2 being independent, substituted or unsubstituted. It may be selected from cyclopentadienyl (Cp), indenyl, and fluorenyl, which may be partially hydrogenated. A, if present, in preferred embodiments dialkylsilyl, dialkylmethyl, diphenylsilyl or diphenylmethyl, ethylenel (-CH)₂-CH₂), Alkylethylenel (-CR₂-CR₂) (Here, alkyl is independent, C₁~ C₁₆It can be selected from alkyl radicals or phenyl, trill, xsilyl radicals, etc.), and in the formula, each of the two X groups, Xa and Xb, independently halide, OR (R is preferably C).₁~ C₅Alkyl group selected from linear or branched alkyl groups), hydrogen, C₁~ C₁₆It is selected from alkyl or aryl groups, haloalkyl and the like. Generally, relatively more highly substituted metallocenes give higher catalytic productivity and a wider product viscosity range and are therefore more preferred in many cases.

0076Any of the polyalphaolefins is preferably 1.8 or less, preferably 1.7 or less, preferably 1.6 or less, preferably 1.5 or less, preferably 1.4 or less, preferably 1.3 or less, preferably 1.2 or less, as measured by ASTM D1159. It preferably has a bromine value of 1.1 or less, preferably 1.0 or less, preferably 0.5 or less, preferably 0.1 or less. If desired, the polyalphaolefin can be hydrogenated to achieve a low bromine value.

0077All m-polyalphaolefins (mPAOs) described herein are in the formula 4: in addition to all regular 1,2-bonds.<chemistry num="2"><img id="000003" he="64" wi="120" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, j, k and m are independently 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, respectively, 20, 21 or 22, where n is an integer from 1 to 350 (preferably 1 to 300, preferably 5 to 50) as measured by proton NMR). It may have a monomer unit represented by.

0078Any of the m polyalphaolefins (mPAOs) described herein is preferably 100,000 or less, preferably 100-80,000, preferably 250-60,000, preferably 280-50,000, preferably 336-40,000 g / mol. Has Mw (weight average molecular weight).

0079Any of the m polyalphaolefins (mPAOs) described herein is preferably Mn (number average molecular weight) of 50,000 or less, preferably 200-40,000, preferably 250-30,000, preferably 500-20,000 g / mol. ).

0080Any of the m polyalphaolefins (mPAOs) described herein is preferably more than 1 and less than 5, preferably less than 4, preferably less than 3, and preferably less than 2.5 molecular weight distributions (MWD-Mw / Mn). ). The mPAO MWD is always a function of fluid viscosity. Alternatively, any of the polyalphaolefins described herein preferably has a Mw / Mn of 1 to 2.5, or 1 to 3.5, depending on the fluid viscosity.

0081The molecular weight distribution (MWD), defined as the ratio of weight average MW to number average MW (= Mw / Mn), is described in "Principles of Polymer Systems" (Ferdin and Rodrigues, McGraw-Hill Book, 1970). It can be measured by gel permeation chromatography (GPC) using a polystyrene standard, as described in 115-144, Chapter 6, The Molecular Weight of Polymers. The GPC solvent was HPLC Grade tetrahydrofuran without stabilizers at a column temperature of 30 ° C, a flow rate of 1 ml / min, and a sample concentration of 1 wt%, and the Column Set was Phenogel 500 A, Linear, 10E 6A. is there.

0082Any of the m-polyalphaolefins (mPAOs) described herein may have a high end tail with a substantially small portion of the molecular weight distribution. Preferably, the mPAO is 5.0% by weight or less of the polymer having a molecular weight of more than 45,000 daltons. Further or / or, the amount of mPAO having a molecular weight of more than 45,000 daltons is 1.5% by weight or less, or 0.10% by weight or less. Further or / or, the amount of mPAO having a molecular weight of more than 60,000 daltons is 0.5% by weight or less, or 0.20% by weight or less, or 0.1% by weight or less. Mass fractions with a molecular weight of 45,000-60,000 can be measured by GPC as described above.

0083In a preferred embodiment of the invention, any PAO described herein is below 0 ° C (as measured by ASTM D97), preferably below -10 ° C, preferably below 20 ° C. Preferably less than -25 ° C, preferably less than -30 ° C, preferably less than -35 ° C, preferably less than -50 ° C, preferably -10 ° C to -80 ° C, preferably -15 ° C. It may have a pour point of ~ -70 ° C.

0084Polyalphaolefins produced using metallocene catalysis are about 1.5 to about 5,000 cSt, preferably about 2 to about 3,000 cSt, preferably about 3 cSt to about 1,000 cSt, more preferably, as measured by ASTM D445. It may have kinematic viscosities from about 4 cSt to about 1,000 cSt, more preferably from about 8 cSt to about 500 cSt at 100 ° C.

0085PAOs useful in the present invention include those produced by the processes disclosed in US Pat. No. 4,827,064 and US Pat. No. 4,827,073. Manufactured using low valence state chromium catalysts, these PAO materials have highly desirable properties to be useful as lubricating base oils and, at higher viscosity grades, as VI (or viscosity index) improvers. Is a polymer olefin oligomer characterized by a very high viscosity index that gives them. They are referred to as high viscosity index PAO or HVI-PAO. High viscosity PAO materials with relatively low molecular weight have been found to be useful as lubricating oil bases, but higher viscosity PAOs, typically above 100 cSt, for example in the range 100-1,000 cSt, are conventional PAOs and It has been found to be very effective as a viscosity index improver for other synthetic and mineral oil-derived base oils.

0086Various modifications and variations of these high-viscosity PAO materials are also mentioned in the following U.S. Pat. Nos.: 4,990,709, 5,254,274, 5,132,478, 4,912,272, 5,264,642: It is described in the specification, No. 5,243,114, No. 5,208,403, No. 5,057,235, No. 5,104,579, No. 4,943,383, and No. 4,906,799. These oligomers can be briefly summarized as being produced by 1-olefin oligomerization in the presence of a metal oligomerization catalyst, which is a supported metal in a low valence state. Preferred catalysts include low valence state chromium on a silica carrier prepared by reduction of chromium using carbon monoxide as a reducing agent. Oligomerization is carried out at a temperature selected according to the desired viscosity for the resulting oligomer, as described in US Pat. Nos. 4,827,064 and 4,827,073. Higher viscosity materials are described in US Pat. No. 5,012,020 and US Pat. No. 5,146,021 where oligomerization temperatures below about 90 ° C are used to produce higher molecular weight oligomers. It may be manufactured as follows. In all cases, after hydrogenation, when necessary to reduce residual unsaturated, oligomers, as defined in US Pat. Nos. 4,827,064 and 4,827,073. ). In general, HVI-PAOs typically have viscosities in the range of about 12-5,000 cSt.

0087In addition, HVI-PAO is generally referred to as: C₃₀~ C₁₃₀₀Hydrocarbons can be characterized by one or more having a branching fraction of less than 0.19, a weight average molecular weight of 300-45,000, a number average molecular weight of 300-18,000, and a molecular weight distribution of 1-5. Especially preferable HVI-PAO is 5 ~ 5000mm²A fluid with a viscosity of 100 ° C in the range / second. In another embodiment, the viscosity of the HVI-PAO oligomer measured at 100 ° C is 3 mm.²/ Sec ~ 15,000mm²It is in the range of / second. In addition, 3mm²/ Sec ~ 5000mm²A fluid with a viscosity at 100 ° C / sec has a VI calculated by ASTM method D2270 over 130. Usually they are in the range 130-350. All fluids have a pour point below -15 ° C.

0088HVI-PAO is C₆~ C₂₀It can be further characterized as a hydrocarbon composition comprising a polymer or oligomer produced from the 1-alkene, taken from the group consisting of 1-alkenes, either alone or in the form of a mixture. Examples of raw materials are 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc., or C.₆~ C₁₄1-Alkene mixture or C₆~ C₂₀1-Alkene, C₆And C₁₂1-Alkene, C₆And C₁₄1-Alkene, C₆And C₁₆1-Alkene, C₆And C₁₈1-Alkene, C₈And C₁₀1-Alkene, C₈And C₁₂1-Alkene, C₈, C₁₀And C₁₂1-Alkenes, as well as other suitable combinations of mixtures.

0089Lubricating oil products usually boil below 600 ° F, or C₂₀Any low molecular weight compositions, such as those with less than carbon atoms, are distilled to remove them if they are produced from the polymerization reaction or brought in from the starting material.

0090Lubricating oil fluids produced directly from polymerization or oligomerization processes usually have unsaturated double bonds or an olefin molecular structure. The amount of double bond or unsaturated or olefinic components is measured by several methods such as bromine value (ASTM D1159), bromine index (ASTM D2710), or other suitable analytical methods such as NMR, IR. be able to. The amount of double bonds or olefin composition is present in some factors-degree of polymerization, the amount of hydrogen present during the polymerization process and the amount of other accelerators involved in the termination step of the polymerization process, or in the process. Depends on other reagents. Usually, the amount of double bonds or olefin components is reduced by a higher degree of polymerization, a higher amount of hydrogen gas present in the polymerization process, or a higher amount of accelerator involved in the termination step.

0091Like other PAOs, the oxidative stability and light or UV stability of HVI-PAO fluids improve as the amount of unsaturated double bonds or olefin content decreases. Therefore, the polymers need to be further hydrogenated if they have a high degree of unsaturatedness. Fluids with a bromine value of less than 5, as measured by ASTM D1159, are typically suitable for high quality base oil applications. Of course, the lower the bromine value, the better the lubricating oil quality. Fluids with a bromine value of less than 3 or 2 are common. The most preferred range is less than 1 or less than 0.1. Hydrogenation methods for reducing unsaturation are well known in the literature (US Pat. No. 4,827,073, Example 16). In some HVI-PAO products, fluids produced directly from polymerization already have very low degrees of unsaturation, such as those with viscosities greater than 150 cSt at 100 ° C. They have a bromine value of less than 5 or even below 2. In these cases, it can be used as is without hydrogenation, or it can be hydrogenated to further improve the base oil properties.

0092Regardless of the process or technique used to make them, if the PAO fluid is used as the only fluid or one of the mixtures that make up the primary base oil of the bimodal mixture useful in the present invention. The PAO fluid is a low kinematic fluid, 2-16 mm²/ Sec, preferably 2-12 mm²KV PAO at 100 ° C in the range of / sec.

0093Low kinematic fluids can be composed of a single base oil that meets the listed kinematic viscosity levels or can be composed of two or more base oils / oils, each of which meets the listed kinematic viscosity limits. it can. In addition, for low kinematic fluids, the resulting mixture blend is 2 to 16 mm listed as the viscosity range of the first low kinematic substrate oil.²One or more high kinematic substrate oils / oils, eg, 100 mm at 100 ° C, provided that they exhibit a target low kinematic viscosity of / sec.²16 mm at 100 ° C, such as base oil / oil with kinematic viscosity of / sec or more²One or more low viscosity base oils / oils combined with kinematic base oils / oils above / second, eg 2-16 mm at 100 ° C²It can be composed of a base oil / oil mixture with kinematic viscosities in the range of / sec.

0094The secondary oil used in the bimodal blend is a high kinematic group IV fluid, ie at least 38 mm.²/ Sec, preferably 38-1200 mm²/ Sec, more preferably 38-600 mm²/ Sec, even more preferably 38-300 mm²/ Sec, most preferably 38-150 mm²PAO of kinematic viscosity at 100 ° C in the range of / sec.

0095When discussing PAO, the name PAO, for example PAO 150, is nominally 150 mm.²Means PAO of kinematic viscosity at 100 ° C / sec.

0096For the second high kinematic viscosity oil, it can consist of a single PAO base oil / oil that meets the listed kinematic viscosity limits, or it can be composed of two types, each of which meets the listed kinematic viscosity limits. It may be composed of the above PAO base oil / oil. Conversely, this second high kinematic base oil / oil has a resulting mixture blend of at least 38 mm at 100 ° C.²One or more lower kinematic PAO base oils / oils mixed with one or more high kinematic PAO base oils / oils, provided that the target high kinematic viscosity of / second is met. For example, 38 mm at 100 ° C²It can be a base oil / oil mixture with a kinematic viscosity of less than / sec.

0097Such higher kinematic PAO fluids can be produced using the same techniques listed above for the production of low kinematic PAO fluids (first oil of bimodal mixture).

0098Preferably, the second fluid of the bimodal mixture, the high kinematic PAO fluid, is produced using metallocene catalysis or the process described in US Pat. No. 4,827,064 or US Pat. No. 4,827,073. To.

0099Regardless of the technique or process used to make PAO, the PAO fluid used as the second base oil for the bimodal blend is at least 38 mm.²High kinematic PAO with KV at 100 ° C / sec.

0100The present invention is at least 30 mm between the first and second base oils of the bimodal blend.²Two different base oils, 2-16 mm at 100 ° C, provided there is a KV difference of / sec²/ Sec, preferably 2-12 mm²At least 38 mm at 100 ° C with one or more Group II, Group III or Group IV base oils, preferably Group III or Group IV base oils, having a KV of / sec.²Achieve that reduction in traction factor with a lubricant containing a bimodal blend with a second, one or more Group IV base oils with a KV of / sec.

0101The reduction in traction factor using the bimodal base oil blends listed above is due to one or more alkaline and / or alkaline earth metals, preferably alkaline earth metals, as previously provided herein. More preferably it depends on the required presence of calcium, phenolate, sulfonate, salicylate or carboxylate detergents. The detergent does not have to be a single metal salt, but in a mixture of metal salts, eg, simply, but not limited to, a mixture of sodium and / or lithium and / or calcium and / or magnesium salts. There can be.

0102In the present invention, it has been found that the traction coefficients at different surface velocities are improved by using various combinations of primary and secondary base oils and detergents.

0103For surface speeds of at least 3 mm / sec, preferably at least 10 mm / sec, the base oil of the lubricant is 2-16 mm.²/ Sec, preferably 2-12 mm²One or more selected from the group consisting of Group II base oils, Group III base oils and Group IV base oils, preferably Group III and Group IV base oils, more preferably Group III base oils having kinematic viscosities at 100 ° C / sec. First base oil, which is oil, and at least 38 mm²/ Sec, preferably 38-1200 mm²/ Sec, more preferably 38-600 mm²/ Sec, even more preferably 38 mm²/ Sec to 300 mm²Less than / sec, most preferably 38-150 mm²A second base oil selected from one or more oils selected from the group consisting of Group IV base oils with kinematic viscosity at 100 ° C / sec, and over 6% by weight to 40% by weight based on the active ingredient. Alkaline and / or alkaline earth metals, preferably alkaline earth metals, more preferably calcium salicylates, phenolates, carboxys, preferably in amounts of 8-40% by weight, more preferably 10-30% by weight. Rate, sulfonate, alkaline and / or alkaline earth metal, preferably alkaline earth metal, more preferably a mixture of calcium salicylate and phenolate or alkaline and / or alkaline earth metal, preferably alkaline earth metal, more A bimodal blend with a detergent selected from calcium phenolates and carboxylates, preferably mixtures of phenolates, salicylates and carboxylates and mixtures of phenolates and carboxylates or mixtures of phenolates and salicylates, wherein. The weight ratio of phenolate to carboxylate or the weight ratio of phenolate to salicylate for the detergent mixture is 6: 1 to 1: 6, preferably 3: 1 to 1: 3, more preferably 2: 1. ~ 1: 2, most preferably 1: 1. Based on the total weight of the lubricant, the lubricant should be at least 5 mg KOH / g, preferably 40-70 mg KOH / g, more preferably 40-70 mg KOH / g TBN, and 13-30 mm at 100 ° C.²/ Sec, preferably 16-30 mm²/ Sec, more preferably 18-25 mm²/ Sec, most preferably 20-25 mm²Has kinematic viscosity of / sec.

0104In another embodiment, for a surface velocity of at least 3 mm / sec, preferably at least 10 mm / sec, the base oil is 2-16 mm at 100 ° C.²/ Sec, preferably 2-12 mm²First base oil, one or more selected from the group consisting of Group II base oils, Group III base oils and Group IV base oils, preferably Group III base oils, with kinematic viscosities of / sec, and 38 mm at 100 ° C.²/ Sec to 300 mm²Less than / sec, preferably 38-250 mm²/ Sec, more preferably 38-150 mm²Over 6% by weight and up to 40% by weight, preferably 8 based on the total weight of the second base oil, selected from one or more oils selected from Group IV base oils with a kinematic viscosity of / sec, and the lubricating oil. ~ 40% by weight, more preferably 10-30% by weight, even more preferably 12-25% by weight of alkaline and / or alkaline earth metal, preferably alkaline earth metal, more preferably a mixture of calcium, sulfonate, or Alkaline and / or alkaline earth metals, in which the weight ratio of phenolate to sulfonate is in the range of 5: 1 to 1: 3, preferably 4: 1 to 1: 2, most preferably 4: 1 to 1: 1. A bimodal blend with a detergent selected from a mixture of alkaline earth metals, more preferably calcium, phenolates and sulfonates, the lubricating oil is at least 5 mg KOH / g, preferably 40-100 mg KOH. / g, more preferably 40-70 mg KOH / g TBN, and 13-30 mm at 100 ° C²/ Sec, 16 ~ 30mm²/ Sec, more preferably 18-25 mm²Has kinematic viscosity of / sec.

0105In another embodiment, the base oil of the lubricating oil is 100 ° C. for a surface speed of at least 30 mm / sec, preferably at least 60 mm / sec, more preferably at least 75 mm / sec, and even more preferably at least 100 mm / sec. 2 ~ 16mm²/ Sec, preferably 2-12 mm²First base oil, which is one or more selected from the group consisting of Group II base oil, Group III base oil and Group IV base oil, preferably Group III base oil, having kinematic viscosities of / sec, and at least at 100 ° C. 38mm²/ Sec, preferably 38-1200 mm²/ Sec, more preferably 38-600 mm²/ Sec, even more preferably 38-300 mm²/ Sec, most preferably 38-100 mm²A second base oil selected from one or more oils selected from Group IV base oils with a kinematic viscosity of / sec, and more than 6% by weight to 40% by weight, preferably 8-40%, based on the weight of the lubricating oil. %%, More preferably 10-30% by weight, most preferably 12-25% by weight (active ingredient) of alkaline and / or alkaline earth metals, preferably alkaline earth metals, more preferably calcium, salicylates, phenolates. , A bimodal blend with detergents selected from sulfonates, carboxylates and mixtures thereof, the lubricating oil is at least 5 mg KOH / g, preferably 40-100 mg KOH / g, more preferably 40-70 mg. TBN of KOH / g, and 6 ~ 30mm at 100 ° C²/ Sec, preferably 8-25 mm²/ Sec, more preferably 12-20 mm²Has kinematic viscosity of / sec.

0106The method can use an engine lubricating oil containing additional performance additives, provided that the base oil contains the essential bimodal blend base oil and the cleaning agent. As shown, the cleaning agents used are alkaline and / or alkaline earth metals, preferably alkaline earth metals, more preferably calcium, salicylates, phenolates, sulfonates, used alone or in various combinations. It is a carboxylate. These cleaning agents can be low, medium or high TBN cleaning agents, that is, cleaning agents having a base value in the range as high as about 5 to 500 mg KOH / g, preferably about 5 to about 400 mg KOH / g. Is.

0107Formulated lubricants useful in the present invention include dispersants, additional cleaning agents, corrosion inhibitors, rust inhibitors, metal defoamers, other anti-wear and / or extreme pressure additives, anti-sticking agents, etc. Wax modifiers, viscosity index improvers, viscosity modifiers, fluid loss additives, seal softeners, other friction improvers, lubricants, stain inhibitors, color formers, defoamers, emulsion destroyers, emulsifiers, boosters It may further contain one or more of other commonly used lubricating oil performance additives including, but not limited to, densifying agents, wetting agents, gelling agents, pressure-sensitive agents, colorants and the like. For a review of many commonly used additives, see Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0. See also "Lubricant Additives" by MWRanney, published by Noyes Data Corporation of Parkridge, NJ (1973).

0108The type and amount of performance additives used in the lubricating oil composition in combination with the present invention is not limited by the examples provided herein by way of example.

0109Viscosity improver Viscosity improvers (also known as viscosity index adjusters, and VI improvers) provide hot and cold operability to lubricants. These additives increase the viscosity of the oil composition and increase the film thickness at elevated temperatures, while exerting a limited effect on the viscosity at low temperatures.

0110Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both viscosity index improvers and dispersants. Typical molecular weights of these polymers are from about 1,000 to 1,000,000, more typically from about 2,000 to 500,000, and even more typically from about 2,500 to 200,000.

0111Examples of suitable viscosity improvers are polymers and copolymers of methacrylates, butadienes, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity improver. Another suitable viscosity index improver is polymethacrylate (eg, a copolymer of various chain length alkyl methacrylates), some of which formulations also serve as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of various chain length acrylates). Specific examples include 50,000-200,000 molecular weight styrene-isoprene or styrene-butadiene-based polymers.

0112The amount of viscosity modifier is zero to 10% by weight, preferably zero to 6% by weight, more preferably zero to 4% by weight, based on the active ingredient and depending on the specific viscosity modifier used. It may be a range.

0113Antioxidant Typical antioxidants include phenolic antioxidants, amine-based antioxidants and oil-soluble copper complexes.

0114Phenolic antioxidants include sulfurized and non-sulphurized phenolic antioxidants. As used herein, the term "phenolic" or "phenolic antioxidant" refers to an aromatic ring that itself may be a monocyclic, eg, benzyl, or polycyclic, eg, a naphthylyl and a spiro aromatic compound. Includes compounds in which one or more hydroxyl groups are attached. Thus, the "phenolic form" is linked by phenol itself, catechol, resorcinol, hydroquinone, naphthol, etc., as well as their alkyl or alkenyl and alkyl sulfide or alkenyl derivatives, and alkylene bridges, sulfur bridges or oxygen bridges as such. Includes bisphenol-type compounds, including various biphenol compounds. Examples of the alkylphenol include mono- and poly-alkyl or alkenylphenols having an alkyl or alkenyl group containing about 3 to 100 carbons, preferably 4 to 50 carbons, and sulfide derivatives thereof. The number of alkyl or alkenyl groups present ranges from 1 to the available unsatisfied bond value of the aromatic ring that remains after counting the number of hydroxyl groups attached to the aromatic ring.

0115In general, therefore, phenolic antioxidants have the general formula: (R)_x-Ar- (OH)_yMay be represented by, where Ar is<chemistry num="3"><img id="000004" he="121" wi="121" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Selected from the group consisting of In the formula, R is C₃~ C₁₀₀Alkyl or alkenyl group, sulfur substituted alkyl or alkenyl group, preferably C₄~ C₅₀Alkyl or alkenyl group or sulfur substituted alkyl or alkenyl group, more preferably C₃~ C₁₀₀Alkyl or sulfur substituted alkyl groups, most preferably C₄~ C₅₀Alkyl group, R^gIs C₁~ C₁₀₀Alkylene or sulfur substituted alkylene group, preferably C₂~ C₅₀An alkylene or sulfur substituted alkylene group, more preferably C₂~ C₂An alkylene or sulfur-substituted alkylene group, y is at least 1 to the available valency of Ar, x is the range from 0 to the available valency of Ar-y, and z is 1 ~ The range is 10, n is the range 0-20, m is 0-4, p is 0 or 1, preferably y is the range 1-3, x is 0-3. It is a range, z is a range of 1 to 4, n is a range of 0 to 5, and p is 0.

0116Preferred phenolic antioxidant compounds are hindered phenolic compounds containing sterically hindered hydroxyl groups, including their derivatives of dihydroxyarule compounds in which the hydroxyl groups are at the o- or p-position of each other. As a typical phenolic antioxidant, C₁Examples include hindered phenols substituted with + alkyl groups and alkylene bond derivatives of these hindered phenols. Examples of this type of phenolic material 2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl- 4-Heptylphenol; 2,6-di-t-butyl-4-dodecylphenol; 2-methyl-6-t-butyl-4-heptylphenol; 2-methyl-6-t-butyl-4-dodecylphenol; 2,6-di-t-butyl-4 methylphenol; 2,6-di-t-butyl-4-ethylphenol; and 2,6-di-t-butyl-4 alkoxyphenol.

0117Phenolic antioxidants are well known in the lubrication industry and are well known in the lubrication industry: Ethanox® 4710, Irganox® 1076, Irganox® L1035, Irganox® 1010, Irganox® L109, Commercial examples such as Irganox® L118 and Irganox® L135 are familiar to those skilled in the art. The above are provided for illustrative purposes only with respect to the types of phenolic antioxidants that can be used and are not limiting.

0118As an aromatic amine antioxidant, the following molecular structure:<chemistry num="4"><img id="000005" he="58" wi="77" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R^zIs hydrogen or C₁~ C₁₄Linear or C₃~ C₁₄Branched alkyl group, preferably C₁~ C₁₀Linear or C₃~ C₁₀Branched alkyl groups, more preferably linear or branched C₆~ C₈And n is an integer in the range 1-5, preferably 1) Examples thereof include phenyl-α-naphthylamine represented by. A specific example is Irganox L06.

0119For other aromatic amine antioxidants, formula R⁸R⁹R¹⁰N [in the formula, R⁸Is an aliphatic, aromatic or substituted aromatic group, R⁹Is an aromatic or substituted aromatic group, R¹⁰Is H, alkyl, aryl or R¹¹S (O)_xR¹²(Here, R¹¹Is an alkylene, alkenylene, or aralkylene group, R¹²Is a higher alkyl group, or an alkenyl, aryl, or alkalil (or alkylaryl) group, where x is 0, 1 or 2)] other alkylated and dealkylated, such as aromatic monoamines. Aromatic amines can be mentioned. Aliphatic group R⁸May contain from 1 to about 20 carbon atoms, preferably from about 6 to 12 carbon atoms. Aliphatic groups are saturated aliphatic groups. Preferably R⁸And R⁹Both are aromatic or substituted aromatic groups, and the aromatic group may be a condensed ring aromatic group such as naphthyl. Aromatic group R⁸And R⁹May be attached to other groups such as S.

0120A typical aromatic amine antioxidant has an alkyl substituent of at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. In general, aliphatic groups will not contain more than about 14 carbon atoms. General types of such additional amine antioxidants that may be present include diphenylamine, phenothiazine, imidedibenzyl and diphenylphenylenediamine. Two or more mixtures of such other additional aromatic amines may also be present. Polymeramine antioxidants can also be used.

0121Another class of antioxidants used in lubricating oil compositions and that may be present in addition to the required phenyl-α-naphthylamine is an oil-soluble copper compound. Any suitable oil-soluble copper compound may be mixed into the lubricating oil. Examples of suitable copper antioxidants include copper dihydrocarbylthio- or dithio-phosphate and copper salts of carboxylic acids (naturally occurring or synthetic). Other suitable copper salts include copper dithiocarbamate, sulfonate, phenolate, and acetylacetonate. Basic, neutral, or acidic copper Cu (I) and / or Cu (II) salts derived from alkenyl succinic acid or acid anhydrides are known to be particularly useful.

0122Such antioxidants may be used in an amount of about 0.10-5% by weight, preferably about 0.30-3% by weight (on arrival basis).

0123Dispersant Oil-insoluble oxidative by-products are produced throughout engine operation. Dispersants help keep these by-products in solution, thus reducing their deposition on metal surfaces. The dispersant may be ash-free or ash-forming in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic substances that do not form virtually any ash when burned. For example, metal-free or boronized metal-free dispersants are considered ashless. In contrast, the metal-containing detergents discussed above form ash on combustion.

0124Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. Polar groups typically contain at least one element of nitrogen, oxygen, or phosphorus. A typical hydrocarbon chain contains 50-400 carbon atoms.

0125A particularly useful class of dispersants are alkenyl succinic acid derivatives, typically produced by the reaction of long chain substituted alkenyl succinic acid compounds, usually substituted succinic anhydride, with polyhydroxy or polyamino compounds. The long chain group that constitutes the lipophilic portion of the molecule that provides solubility in oil is usually a polyisobutylene group. Many examples of this type of dispersant are well known commercially and in the literature.

0126Hydrocarbyl-substituted succinic acid compounds are a popular dispersant. In particular, succinimide, a succinate ester, or a succinate produced by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in a hydrocarbon substituent with at least 1 equivalent of an alkylene amine. Esteramides are particularly useful.

0127Succinimides are formed by the condensation reaction of alkenyl succinic anhydride and amine. The molar ratio can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1.

0128The succinate ester is formed by the condensation reaction of alkenyl succinic anhydride with an alcohol or polyol. The molar ratio can vary depending on the alcohol or polyol used. For example, the condensation product of alkenyl succinic anhydride and pentaerythritol is a useful dispersant.

0129The succinate ester amide is formed by the condensation reaction of alkenyl succinic anhydride and alkanolamine. For example, suitable alkanolamines include polyalkenyl polyamines such as ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyethylene polyamines. One example is propoxylated hexamethylenediamine.

0130The molecular weight of alkenyl succinic anhydride will typically range from 800 to 2,500. The above products can be post-reacted with various reagents such as carboxylic acids such as sulfur, oxygen, formaldehyde, oleic acid, and boron compounds such as borate esters or hyperboration dispersants. The dispersant can be boronized with about 0.1 to about 5 moles of boron per mole of the dispersant reaction product.

0131The Mannich base dispersant is made from the reaction of alkylphenols, formaldehyde, and amines. Processing aids and catalysts, such as oleic acid and sulfonic acid, can also be part of the reaction mixture. The molecular weight of alkylphenols ranges from 800 to 2,500.

0132A typical high molecular weight fatty acid modified Mannich condensation product is a high molecular weight alkyl-substituted hydroxy aromatic compound or HN (R).₂It can be produced from a group-containing reactant.

0133Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenols, polybutylphenols, and other polyalkylphenols. These polyalkylphenols are BFs of phenols in high molecular weight polypropylene, polybutylene, and other polyalkylene compounds for providing alkyl substituents on the benzene ring of phenols having an average molecular weight of 600-100,000.₃It can be obtained by alkylation in the presence of an alkylation catalyst, such as.

0134HN (R)₂Examples of group-containing reactants are alkylene polyamines, mainly polyethylene polyamines. At least one HN (R) suitable for use in the manufacture of Mannich condensation products₂Other representative organic compounds containing groups are well known and mono- and di-aminoalkanes and their substitution analogs such as ethylamine and diethanolamine; aromatic diamines such as phenylenediamine, diaminonaphthalene; Includes heterocyclic amines such as morpholine, pyrrol, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substitution analogs.

0135Examples of alkylene polyamine reactants are ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, heptaethyleneoctamine, octaethylenenonaamine, nonaethylenedecamine, and decaethylene. Ethylenediamine and the above-mentioned equation H₂N- (Z-NH-)_nExamples thereof include a mixture of H's such amines having a nitrogen content corresponding to an alkylene polyamine, where Z in the above formula is divalent ethylene and n is 1-10. Propylene diamines and corresponding propylene polyamines such as di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamine are also suitable reactants. The alkylene polyamine is usually obtained by reacting ammonia with a dihaloalkane, such as a dichloroalkane. Thus, alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 2 to 6 moles of carbon atoms and 1 to 10 moles of dichloroalkanes having chlorine on different carbons are suitable alkylene polyamine reactants. ..

0136Aldehyde reactants useful in the production of polymer products useful in the present invention include aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or formaldehyde-producing reactants are preferred.

0137Preferred dispersants include mono-succinimide, bis-succinimide, wherein hydrocarbylsuccinimide is derived from a hydrocarbylene group such as polyisobutylene having about 500 to about 5000 Mn or a mixture of such hydrocarbylene groups. Included and / or those derivatives from a mixture of mono- and bis-succinimide, including boring and non-boronized succinimide. Other preferred dispersants include succinates and amides, alkylphenol-polyamine bond Mannich adducts, capped derivatives thereof, and other related components. Such additives are used in an amount of about 0.1-20% by weight, preferably about 0.1-8% by weight, more preferably about 1-6% by weight (on arrival basis) relative to the weight of the total lubricant. You may.

0138Pour point depressant Conventional pour point depressants (also known as lubricating oil fluidity improvers) may also be present. Pour point depressants may be added to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable flow point lowering agents are alkylated naphthalenes, polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffin waxes with aromatic compounds, vinyl carboxylate polymers, and dialkyl fumarate and fatty acids. A terpolymer of vinyl ester and allyl vinyl ether can be mentioned.

0139Such additives may be used in an amount of about 0.0 to 0.5% by weight, preferably about 0 to 0.3% by weight, more preferably about 0.001 to 0.1% by weight on an arrival basis.

0140Corrosion inhibitor / metal inactivating agent Corrosion inhibitors are used to reduce the decomposition of metal parts that are in contact with the lubricating oil composition. Suitable corrosion inhibitors include arylthiazine, alkyl-substituted dimercaptothiodiazol thiadiazoles and mixtures thereof.

0141Such additives are about 0.01-5% by weight, preferably about 0.01-1.5% by weight, more preferably about 0.01-0.2% by weight, even more preferably about 0.01-%, based on the total weight of the lubricating oil composition. It may be used in an amount of 0.1% by weight (on an arrival basis).

0142Seal compatible additive The seal adaptant helps to swell the elastomer seal by causing a chemical reaction in the fluid or a physical change in the elastomer. Suitable seal fillers for lubricants include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzylphthalate), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3% by weight, preferably about 0.01 to 2% by weight, on an arrival basis.

0143Defoamer A defoamer may be added favorably to the lubricating oil composition. These reagents inhibit the formation of stable foam. Silicones and organic polymers are typical defoamers. Polysiloxanes, such as silicone oils or polydimethylsiloxanes, provide defoaming properties. Defoamers are commercially available and may be used in customary small amounts with other additives such as emulsifying disruptors; usually the amount of these additives combined is the lubricant composition. Less than 1%, preferably 0.001 to about 0.5% by weight, more preferably about 0.001 to about 0.2% by weight, even more preferably about 0.0001 to 0.15% by weight (on arrival basis), based on the total weight of the object.

0144Inhibitors and rust preventive additives Anti-corrosion additives (or anti-corrosion agents) are additives that protect the surface of the metal to be lubricated from chemical attacks by water or other contaminants. One type of rust preventive additive is a polar compound that preferentially moistens the metal surface and protects it with an oil film. Another type of rust preventive additive absorbs water by incorporating it into a water-in-oil emulsion so that only the oil touches the surface. Moreover, another type of rust preventive additive chemically adheres to the metal to create a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01-5% by weight, preferably about 0.01-1.5% by weight, on an arrival basis.

0145Anti-wear additives can also be present advantageously. Anti-wear additives are exemplified by metal dithiophosphates, metal dithiocarbamates, metal dialkyldithiophosphates, metal zantates, where the metal can be zinc or molybdenum. Trickresyl phosphate is another type of anti-wear additive. Such anti-wear additives can be present in an amount of about 0.05-1.5% by weight, preferably about 0.1-1.0% by weight, more preferably about 0.2-0.5% by weight (on an arrival basis) on an arrival basis. ..<u style="single">The main aspects described in the present specification are shown below.</u><u style="single">1. Two different base oils,</u><u style="single">2 ~ 16mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">With the first base oil, which is one or more oils selected from the group consisting of Group II base oil, Group III base oil and Group IV base oil with kinematic viscosity of / sec.</u><u style="single">At least 38mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">Second base oil selected from one or more oils selected from the group consisting of Group IV base oils with kinematic viscosities of / sec</u><u style="single">It is a bimodal blend with</u><u style="single">The difference in kinematic viscosity between the first base oil and the second base oil in the bimodal blend is at least 30 mm.</u>^{<u style="single">2</u>}<u style="single">Base oil containing a bimodal blend that is / sec, as well as</u><u style="single">Alkaline and / or alkaline earth metal salicylate, phenolate, carboxylate, sulfonate, phenolate at all treatment levels in amounts from 6% to 40% by weight (active ingredient) relative to the total weight of the lubricating oil. Lubricant selected from a mixture of salicylate and a mixture of phenolate and carboxylate</u><u style="single">Including, 13 ~ 30mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">By using a lubricating oil with a kinematic viscosity of / sec and a base value of at least 5 mg KOH / g as the engine oil, by reducing the traction coefficient of the engine oil used to lubricate the engine, the engine oil A way to improve the fuel economy of large low speed, medium and high speed engines that are lubricated and reach a surface speed of at least about 3 mm / sec.</u><u style="single">The above improvements in fuel economy are not bimodal blends or are based solely on Group I and / or Group II base oils or at least 38 mm at 100 ° C.</u>^{<u style="single">2</u>}<u style="single">A method demonstrated by the fact that the traction factor of an engine oil using its bimodal blend is lower than the traction factor of an engine oil containing no Group IV base oil with a KV of / sec.</u><u style="single">2. Two different base oils,</u><u style="single">2 ~ 16mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">With the first base oil, which is one or more oils selected from the group consisting of Group II base oil, Group III base oil and Group IV base oil with kinematic viscosity of / sec.</u><u style="single">At least 38mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">Second base oil selected from one or more oils selected from the group consisting of Group IV base oils with kinematic viscosities of / sec</u><u style="single">It is a bimodal blend with</u><u style="single">The difference in kinematic viscosity between the first base oil and the second base oil in the bimodal blend is at least 30 mm.</u>^{<u style="single">2</u>}<u style="single">Base oil containing a bimodal blend that is / sec, as well as</u><u style="single">Alkaline and / or alkaline earth metal salicylates, phenolates, sulfonates, in which the total amount of cleaning agent used ranges from more than 6% by weight to 40% by weight (active ingredient), based on the total weight of the lubricating oil. A lubricant selected from the group consisting of carboxylates and mixtures thereof</u><u style="single">Including, 6 ~ 30mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">By using a lubricating oil with a kinematic viscosity of / sec and a base value of at least 5 mg KOH / g as the engine oil, by reducing the traction coefficient of the engine oil used to lubricate the engine, the engine oil A way to improve fuel economy for large engines that are lubricated and reach a surface speed of at least about 30 mm / sec.</u><u style="single">The above improvements in fuel economy are not bimodal blends or are based solely on Group I and / or Group II base oils or at least 38 mm at 100 ° C.</u>^{<u style="single">2</u>}<u style="single">A method demonstrated by the lower traction factor of an engine oil using its bimodal blend than the traction factor of an engine oil containing no Group IV base oil with a KV of / sec.</u><u style="single">3. Two different base oils,</u><u style="single"> 2 ~ 16mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">With the first base oil, which is one or more oils selected from the group consisting of Group II, Group III and Group IV base oils with kinematic viscosities of / sec.</u><u style="single">38 to 300 mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">Second base oil selected from one or more oils selected from the group consisting of Group IV base oils with kinematic viscosities less than / sec</u><u style="single">It is a bimodal blend with</u><u style="single">The difference in kinematic viscosity between the first base oil and the second base oil in the bimodal blend is at least 30 mm.</u>^{<u style="single">2</u>}<u style="single">Base oil containing a bimodal blend that is / sec, as well as</u><u style="single">Alkaline and / or alkaline earth metal sulfonates or phenolates and sulfonates in which the total amount of cleaning agent is in the range of more than 6% by weight to 40% by weight (active ingredient) based on the total weight of the lubricating oil. Lubricant selected from the group consisting of mixtures</u><u style="single">Including, 13 ~ 30mm at 100 ° C</u>^{<u style="single">2</u>}<u style="single">Lubricating oils with kinematic viscosities of / sec and a base value of at least 5 mg KOH / g,</u><u style="single">When used as engine oil, it is lubricated by engine oil by reducing the traction coefficient of the engine oil used to lubricate the engine, reaching a surface speed of at least about 3 mm / sec, large low speed, medium speed and It s a way to improve the fuel economy of high-speed engines.</u><u style="single">The above improvements in fuel economy are not bimodal blends or are based solely on Group I and / or Group II base oils or at least 38 mm at 100 ° C.</u>^{<u style="single">2</u>}<u style="single">A method demonstrated by the lower traction factor of an engine oil using its bimodal blend than the traction factor of an engine oil containing no Group IV base oil with a KV of / sec.</u><u style="single">Four. The method according to 1 above, wherein the first base oil is selected from Group III and Group IV base oils.</u><u style="single">Five. The method according to 2 above, wherein the first base oil is selected from Group III and Group IV base oils.</u><u style="single">6. The method according to 3 above, wherein the first base oil is selected from Group III and Group IV base oils.</u><u style="single">7. The method according to any one of 1 to 3 above, wherein the cleaning agent is present in an amount of 8 to 40% by weight (active ingredient).</u><u style="single">8. 8. The kinematic viscosity of the lubricating oil at 100 ° C is 16 to 30 mm.</u>^{<u style="single">2</u>}<u style="single">The method described in 1 above, which is in the range of / second.</u><u style="single">9. The kinematic viscosity of the lubricating oil at 100 ° C is 18 to 25 mm.</u>^{<u style="single">2</u>}<u style="single">The method described in 1 above, which is in the range of / second.</u><u style="single">Ten. The kinematic viscosity of the lubricating oil at 100 ° C is 8 to 25 mm.</u>^{<u style="single">2</u>}<u style="single">The method described in 2 above, which is in the range of / second.</u><u style="single">11. 11. The kinematic viscosity of the lubricating oil at 100 ° C is 16 to 30 mm.</u>^{<u style="single">2</u>}<u style="single">The method described in 3 above, which is in the range of / second.</u><u style="single">12. The kinematic viscosity of the lubricating oil at 100 ° C is 18 to 25 mm.</u>^{<u style="single">2</u>}<u style="single">The method described in 3 above, which is in the range of / second.</u><u style="single">13. The method according to any one of 1 to 3 above, wherein the second base oil is a PAO base oil.</u><u style="single">14. 13. The method according to 13 above, wherein the PAO base oil is produced using a metallocene catalyst.</u><u style="single">15. 15. 13. The method of 13 above, wherein the PAO base oil is characterized by less than 5.0% by weight of a polymer having a molecular weight greater than 45,000 daltons.</u>

<p num="0146">Comparative Examples and Examples A series of engine oils were evaluated for their effect on the traction factor of the base oil composition and detergent type. The engine oil is a base oil blend that uses only commercially available oils (control oil A (Ref. A)) or a combination of a first base oil with a different kinematic viscosity and a second base oil with a different kinematic viscosity. It is either a control oil B (Ref. B)) or a base oil blend in combination with different lubricants or mixtures of detergents at different usages / treatment levels that produce lubricating oils with different kinematic viscosity. All formulations contained a detergent having a base value (BN) of 40 or 70 mg KOH / g. The traction coefficient was measured using the MTM Traction Rig, which is a fully automatic Mini Traction Machine traction measuring device. This rig is manufactured by PCS Instruments and is a Model Identified as MTM. The test specimens and equipment configurations are such that realistic pressures, temperatures and speeds can be achieved without the need for very heavy loads, motors or structures. A small sample of fluid (50 ml) is placed in the test cell and the machine automatically spans various speeds, slide-to-roll ratios, temperatures and loads to create a comprehensive traction map for the test fluid without operational intervention. Operate. The standard test sample is AISI Polished 19.05mm spheres and 50.0mm diameter discs made from 52100 bearing steel. The specimen is designed to be a single-use, disposable item. The sphere is loaded with the disc side back, and the sphere and disc are driven independently by a DC servomotor and drive, enabling highly accurate speed control, especially with low slide / roll ratios. Each specimen is terminally mounted on a shaft in a small stainless steel test fluid bath. Fix the vertical shaft and drive system that support the disc test specimen. However, the shaft and drive system that supports the ball test specimen is supported in a gimbal arrangement so that it can rotate around two orthogonal axes. One axis is perpendicular to the load application direction and the other is perpendicular to the traction force direction. Drive the sphere and the disc in the same direction. Load application and traction force suppression are performed by a high stiffness transducer properly mounted in the gimbal arrangement to minimize overall support system deflection. The output from these force transducers is directly monitored by a personal computer. The traction coefficient is the ratio of the traction force to the applied load. Traction coefficients were measured over various velocities as shown in Figures 1-9. In FIGS. 1-9, the velocity on the x-axis is the entrainment velocity, which is half the sum of the sphere and disk velocities. These entrainment speeds simulate at least a portion of the surface speed range, or surface speed range, that is reached when the engine is running.</p><p num="0147"> The test results presented herein were produced under the following test conditions:</p><p num="0148"><tables num="1"><img id="000006" he="38" wi="109" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></tables> Two different machines of the same model, Model MTM, were used in these evaluations and the machine identity (Machine 1 or Machine 2) used is shown in the figure.</p><p num="0149"> Lubricating oil<u style="single">table 1</u>as well as<u style="single">Table 1 (continued)</u>Described in.</p><p num="0150"><tables num="2"><img id="000007" he="228" wi="158" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0151"><tables num="3"><img id="000008" he="221" wi="158" file="JP5852012B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0152"> In addition to different base oils, mixtures of base oils and detergents, all formulations also contain the same amount of dispersant, antioxidant in all formulations, except for control oil B, which contained no additives. And contained other additives such as extreme pressure / anti-wear additives.</p><p num="0153"> The effect of compounding variables on lubricating oil performance in terms of traction coefficients at different velocities is understood by reference to the figures. For those oils identified as containing Group III oils below, the Group III oils used were hydrodesulfurized and denitrified with slack wax to remove any sulfur and nitrogen compounds. It was a slack wax isomer produced by then hydrogen isomerizing slack wax and then hydrogenating and purifying.</p><p num="0154"> Group IV base oil was PAO. The kinematic viscosity is specified by name, for example, PAO 150, PAO is nominally 150 mm.²Identifies to have KV at 100 ° C / sec.</p><p num="0155"> In FIG. 1, oils IA, IB, II and III are compared to control oil A. In all four formulations and control oils, control oil A is a blend of Group I base oil and PIB, while oils IA-III contain a blend of Group III base oil and Group IV base oil (PAO). Has the same cleaning agents and other additives, except that</p><p num="0156"> From Figure 1, Group III (6.5 mm)²/ Second) / Group IV (150mm)²It can be seen that all of the oils, IA-III, blended with the bimodal blend of (/ sec) produced a large improvement in traction coefficient compared to control oil A at speeds of 80 mm / sec and above. The effect on the traction coefficient at different rates with respect to control oil A also depends on the final kinematic viscosity of the blended oil and the kinematic viscosity of the second high viscosity oil of the blend.</p><p num="0157"> 20mm²For blended oils IA and IB with kinematic viscosity blends of / sec and mixtures of phenolate and sulfonate cleaners, the traction factor is 150 mm for the second high viscosity component of the blend.²When having a kinematic viscosity at 100 ° C / sec, it was lower than that of the control oil at all speeds.</p><p num="0158"> 16mm²For blended oil II with kinematic viscosity blends at 100 ° C / sec and a mixture of phenolate and sulfonate, the traction factor is more consistent than that of control oil A only at higher speeds of about 60 mm / sec and above. It was low.</p><p num="0159"> Finally, 20mm²A blend of kinematic viscosity at 100 ° C / sec, the second high viscosity oil component of the blend is 300 mm²For Blended Oil III using blends with kinematic viscosities at 100 ° C / sec and containing a mixture of phenolate and sulfonate cleaners, the traction factor is higher rates of about 70 mm / sec and above. Only in was consistently lower than that of control oil A.</p><p num="0160"> In FIG. 2, blended oils IV to VII are compared to each other and to control oil A and control oil B.</p><p num="0161"> Figure 2 shows the effect on the blended oil traction coefficient of a single detergent type at different rates.</p><p num="0162"> All 20mm at 100 ° C²Based on blends with kinematic viscosity of / sec, all Group III (6.5 mm)²/ Second) For blended oils IV-VII, manufactured using the same combination of base oil and Group IV base oil (PAO 150), all containing the same amount of other additives as the single detergent additive alone. It can be seen that the traction coefficients of the blended oils IV, VI and VII were lower than that of control oil A over the entire engine speed range regardless of whether the single detergent was salicylate, carboxylate or phenolate. Blended oils IV, VI and VII were all superior to control oil A over the entire speed range, but the best functioning blended oils contained salicylate (oil IV) and carboxylate (oil VI) detergents.</p><p num="0163"> Blended oils (oil V) containing sulfonate detergents perform better than control oils at low speeds (about 3-60 mm / sec) and show performance fluctuations at higher speeds (about 100 mm / sec and above). It suggests that the formulation is optimal for use only under continuous and faster operating conditions (100 mm / s and above) or continuous low speed operating conditions (3-50-60 mm / s). All blended oils containing salicylate (oil IV), sulfonate (oil V) or carboxylate (oil VI) are slower (approximately 3-12 mm) than control oil B (base oil only).²/ Seconds) worked better.</p><p num="0164"> Figures 3A and 3B show the effects of various blend kinematic viscosities and second oil component kinematic viscosities of blends using the same combination of phenolate and salicylate cleaners on traction coefficients at different rates, and other additives. And the effect of formulation BN is shown.</p><p num="0165"> In Figure 3B, blended oils VIII-A, XI and XII (20-25 mm at 100 ° C)²Blend KV / sec, 40 or 150 mm at 100 ° C²2nd high viscosity oil KV / sec) and blended oil XXX (20mm at 100 ° C)²Blend KV / sec, 150 mm at 100 ° C²40 formula blends BN containing a second high viscosity oil KV of / sec, the same mixture of phenolate and salicylate detergents and other additives, control oils at all rates in terms of reducing traction coefficient It can be seen that the performance was consistently superior to A. Blended oils XI and XII also outperformed control oil B ((Ref. B) base oil only) under low speed (3-10 mm / sec) conditions.</p><p num="0166"> In Figure 3A, blended oils IX-A and IX-B (13 and 16.5 mm at 100 ° C) containing the same mixture of salicylate and phenolate detergents and other additives.²Blend KV / sec, 150 mm at 100 ° C²Second high viscosity oil KV) per second consistently outperforms control oil A only at higher speeds of approximately 50 mm / sec or higher (oil IX-B) or 100 mm / sec or higher (oil IX-A). You can see that it was.</p><p num="0167"> Blended Oil X (20 mm at 100 ° C) containing the same mixture of salicylate and phenolate cleaners and other additives²Blend KV / sec, 300 mm at 100 ° C²Second high viscosity at KV / s) was also consistently superior to control oil A only at higher velocities of about 20 mm / s and above.</p><p num="0168"> Thus, the formulations in Figures 3A and 3B all outperformed Control Oil A at higher speeds, whereas Blended Oils VIII-A, IX-B, XI, XII and XXX were these formulations. All of the oils contain the same mixture of salicylate and phenolate cleaners, and 20-25 mm at 100 ° C.²With kinematic viscosities of / sec and with a second Group IV base oil (PAO 40 or PAO 150) blending component, it is comparable to or better than control oil A over the full velocity range in both figures. It was.</p><p num="0169"> In FIG. 4, the blended oils XIII to XV are compared with each other and with respect to control oil A and control oil B.</p><p num="0170"> Figure 4 uses Group I / Group I and Group IV / Group IV combinations of the same phenolate / salicylate detergent mixture and other additive base oils with different blend kinematic viscosities of 70 BN for all formulations. Shows the effect of this on the traction coefficient at different speeds.</p><p num="0171"> 21 mm at 100 ° C²Only blended oil XIV, which uses a mixture of group IV (PAO 8) base oil and group IV base oil (PAO 40) blended into kinematic viscosity per second, outperforms control oil A in terms of traction factor over the entire speed range. Excellent, but low speed (3-12mm)²Performance was also better than control oil B (base oil only) under (/ sec) conditions.</p><p num="0172"> 22mm²Group I (8mm) blended in / sec²/ Second) / Group I (32mm)²/ Sec) Blended Oil XIII, which uses the same phenolate / salicylate detergent combination in the base oil mixture, outperformed Control Oil A only under low to medium speed (3-50 mm / sec) conditions. .. That is (21mm²13mm at 100 ° C (rather than / sec)²Blended oil XV, which is the same as oil XIV except that it was blended with KV at / sec, outperformed control oil A only under medium to high speed (80 mm / sec and above) conditions.</p><p num="0173"> In FIG. 5, the blended oils XVI, XVII, XVIII and XIX are compared to each other and to control oil A and control oil B.</p><p num="0174"> Figure 5 shows all 70 compound base values, and 20 mm at 100 ° C.²Shows the effect of using the same phenolate / salicylate detergent combination and other additive-containing Group I / Group IV and Group II / Group IV base oil combinations blended at KV / sec.</p><p num="0175"> Blended oil XIX, Group II (3mm)²/ Second) Only formulations using a base oil combination of base oil and Group IV base oil (PAO 40) outperformed Control Oil A in terms of coefficient of friction over the entire speed range. It also has a low to medium speed range (3 to 20 mm)²Performance was superior to control oil B (group III / group IV base oil combination only) at (/ sec).</p><p num="0176"> Blended oil XVIII, which is the same as oil XIX except that the second base oil component is Group IV base oil (PAO 150) (instead of PAO 40), is only available in the medium to high speed range (approximately 20 mm / sec and above). It performed better than control oil A and better than oil XVI (Group I / Group IV formulation). It is 3mm of blended oil XVIII as the first base oil component²/ Second Group II Higher kinematic viscosity group II (12mm) instead of base oil²/ Sec) Same as Oil XVIII except that it uses base oil, Oil XVII has a slighter traction coefficient benefit than Control Oil A under low to medium speed conditions (3-10 mm / sec). It showed very little benefit under high speed (100 + mm / sec) conditions. 12mm²Group II base oils with kinematic viscosities less than / sec are therefore preferred to obtain significant traction coefficient benefits at higher speeds (100 mm / sec and above).</p><p num="0177"> Figures 6A and 6B show that all formulations are BN70, 20 mm at 100 ° C.²Group III (6.5mm) blended with / sec blend KV²/ Second) Comparison of different phenolate / co-cleaner blends in the base oil / Group IV base oil (PAO 150) mixture, showing comparisons to each other and to control oils A and B.</p><p num="0178"> Figure 6A shows that both oil IA (phenolate / sulfonate) and oil VIII-A (phenolate / salicylate) have traction compared to control oil A (phenolate / sulfonate in Group I / PIB blend) over the entire speed range. It is shown that it provides a large improvement in coefficient. Oil VIII-A is low to medium speed (about 3 to 80-90 mm)²/ Second), which is superior to oil IA.</p><p num="0179"> Figure 6B shows Group III (6.5 mm)²It is shown that the phenolate / carboxylate detergent combination in the base oil / group IV base oil (PAO 150) blend also provides a significant improvement in traction factor compared to control oil A over the entire speed range. However, under very low speed conditions (about 3-7 mm / sec), the phenolate / carboxylate detergent combination is still effective, but does not offer as much benefit as the phenolate / salicylate combination.</p><p num="0180"> In FIG. 7, blended oils IV, VIII-A, XXI, XXII, XXIII and VII are compared to each other and to control oil A and control oil B.</p><p num="0181"> FIG. 7 shows the effect of varying the amount of salicylate and sulfonate cleaner used in blends containing a combination of phenolate, salicylate and sulfonate cleaner on the traction coefficient. All of these formulations are 20 mm at 100 ° C using the same low KV and higher KV primary and secondary base oils.²Blended to the same kinematic viscosity of / sec. As can be seen, Blended Oil IV, which contains only salicylate cleansers, showed the greatest reduction in traction factor over the entire speed range, but a mixture of salicylate, phenolate and sulfonate cleaners (salicylate is sulfonate cleansers). Those formulations containing (replaced part of the agent) were required to show at least 1.5 wt% salicylate improvement over control oil A at low to medium speeds (3 to 50 mm / sec). It showed a performance that changes with the amount of salicylate present.</p><p num="0182"> Formulations containing salicylate alone or a mixture of salicylate and phenolate or a mixture of sulfonate and phenolate are preferred over formulations containing a mixture of salicylate, phenolate and sulfonate.</p><p num="0183"> In FIG. 8, blended oils VII, XXIV, VIII-A, XXV, XXVI and IV are compared to each other and to control oil A and control oil B.</p><p num="0184"> Figure 8 shows the effect of varying the amount of salicylate detergent relative to the phenolate detergent on the traction factors for the blended KV as well as for the lower KV and higher KV base oils used, otherwise for the same formulation. Is shown. As can be seen, the higher the salicylate / phenolate ratio, the better the traction factor performance. However, maximizing the phenolate concentration in the formulation is important for other performance characteristics.</p><p num="0185"> Blended oil XXV, containing about 7.5% by weight salicylate and 7.4% by weight of phenolate detergent (weight ratio about 1: 1), showed the best overall traction coefficient improvement compared to control oil A in particular. Slightly lowering the salicylate / phenolate ratio in oil VIII-A containing about 4.7% by weight salicylate and 11.5% by weight phenolate (salicylate: phenolate weight ratio about 1: 2.5), oil XXV and oil XXVI The traction coefficient performance deteriorated at a low speed (3 to 10 mm / sec) compared to the above. Therefore, it is desirable to maximize the effect on the traction coefficient by using a salicylate / phenolate detergent blend that uses a phenolate content and a salicylate / phenolate weight ratio of 1: 1 to 1: 2.5.</p><p num="0186"> It must be pointed out that all formulations exceeded control oil A in terms of their effect on their traction coefficients at all speeds, oils VII, XXV, XXVI and IV under low speed conditions (3 ~ It exceeds the traction coefficient of control oil B, base oil only) under 10 mm / sec). 100% Phenolate Formulation (Oil VII), Oil XXIV (2.5 wt% Salicylate / 14.7 wt% Phenolate), Oil VIII-A (Oil VIII-A) It should be pointed out that it provided better traction coefficient performance than 4.7 wt% salicylate and 11.5 wt% phenolate), and oil XXVI (10 wt% salicylate and 3.7 wt% phenolate).</p><p num="0187"> In FIG. 9, blended oils V, VII, XXVII, XXVIII and XXIX are compared to each other and to control oil A and control oil B.</p><p num="0188"> Figure 9 shows the effect of varying the amount of sulfonate detergent relative to phenolate detergent on the traction coefficient of the blended KV as well as the lower KV and higher KV base oils used, otherwise in the same formulation. Is shown. For formulations containing a mixture of sulfonate and phenolate cleaners, the higher the sulfonate / phenolate ratio tested, the better the traction factor performance compared to control oil A at all speeds. is there. However, sulfonate-only detergents are more than control oil A at low speeds (3-12 mm / sec) and high speeds (100 + mm / sec) for all sulfonate oils, oil V, not only because of the absence of phenolates at all. It provides a large traction coefficient benefit, but this benefit is much less than that of oils containing a mixture of phenolate and sulfonate, or none compared to control oil A at medium speeds (20-100 mm / sec). This is not desirable as Figure 9 shows that it is even. The phenolate-only detergent formulation (Oil VII) outperforms the sulfonate / phenolate blend at low to medium speeds (approximately 3-10 mm / sec). Only oil XXIX (6 wt% sulfonate / 5 wt% phenolate) outperforms oil VII at high speeds (100 + mm / sec).</p>