JPH09512584A - Crankcase lubricants for modern heavy duty diesel and gasoline fueled engines - Google Patents

Abstract

  (57) [Summary] Disclosed are lubricants having an ashless dispersant having a TBN of greater than 100, a magnesium source, and an ashless nitrogen-containing TBN source with a metal salt of dihydrocarbyl dithiophosphate. This lubricant comprises a major amount of oil of lubricating viscosity having a sulfated ash content of 0.35 to 2% by mass, and A) an ashless nitrogen-containing dispersant, an ashless nitrogen-containing dispersant viscosity modifier, an oil-soluble aliphatic, A nitrogen-containing TBN source selected from the group consisting of oxyalkyl or arylalkylamines, and mixtures thereof, B) a metal salt of an oil-soluble acid having a TBN greater than 100, C) at least 500 ppm (mass) magnesium, And D) at least one dihydrocarbyl dithiophosphoric acid metal salt. The nitrogen containing TBN source provides the finished lubricant with a TBN of at least about 1.5. The metal salt of the oil soluble acid provides at least about 40% of the total TBN of the composition. At least 50 mol% of the hydrocarbyl groups on the dihydrocarbyl dithiophosphate are second. Overbased magnesium sulfonate can be used as an additive to provide metal salts of oil-soluble acids with TBN greater than 100 and magnesium of at least 500 ppm (mass). The lubricant may be free of aromatic amines having at least two aromatic groups attached directly to the nitrogen. The lubricant may include at least 100 ppm (mass) boron and at least 1000 ppm (mass) phosphorus. The ratio of boron to nitrogen is at least 0.1.

Description

Detailed Description of the Invention   Clan for modern heavy duty diesel and gasoline fueled engines Case lubricant Field of the invention   The present invention relates to crankcase lubricants. In particular, the present invention is useful under a variety of conditions. Induced by soot-related viscosity increase and thermal oxidation while preventing wear and corrosion It relates to a universal lubricant that is effective in minimizing the increase in viscosity. BACKGROUND OF THE INVENTION   A crank that performs properly in one engine under given operating conditions Case lubricants when used in different engines or under different conditions , It does not always perform properly. Theoretically, the lubricant is the engine It is possible to design for each possible combination of Such a strategy is impractical. Because many different types of engines Existing and each engine is used under different conditions. Therefore, A wide range of conditions in different types of engine (eg fuel type, operating load Lubricants that perform well over weight and temperature) are desirable. Crankcase Jun Lubricant design depends on the chemistry added to the lubricating oil base stock to impart the desired properties. Concentrated mixture of chemicals works well over a wide range of different quality base materials It is more complicated in that it must work. Meet these requirements That is extremely difficult. Because the composition is complex and the lubricant works well Testing to determine whether or not It ’s difficult to collect data from field trials because we do n’t have enough control. Because it is.   Achieving the goals imposed by the stricter regulations on vehicle emissions is also more difficult Will be More recently, in North America, diesel fuel used on public roads The maximum allowable concentration of sulfur present in the feed was reduced to 0.05% by weight. APIC New API category defined as G-4 is heavy duty with low sulfur fuel -Regarding the performance of the lubricant. At the same time, the fuel for vehicles traveling on non-public roads Sulfur concentrations can have higher levels. Moreover, like Latin America In some regions, fuel sulfur levels remain high for all applications. Follow A lubricant for use in heavy duty diesel engines Must function to an acceptable degree at a range of sulfur concentrations.   To meet this need, the American Petroleum Institute (American Petroleum Institute) (API) is operated under conditions related to lubrication issues. Test panel designed to verify the performance of lubricants in various engines We have issued a certification certificate for lubricants that have passed the above criteria. Requirements for API authorization In addition to the heavy duty diesel engine manufacturer, Required to pass additional tests before being approved for use by an engine such as Wanting. All requirements for heavy duty diesel engine manufacturers Gasoline fuel engine and heavy duty diesel fuel engine Of the American Petroleum Institute oil supply certification for both Lubricants that meet all of the highest level requirements are often universal oils (u niversal oils).   Many heavy duty diesel lubricants are required to pass Some of the tests include caterpillar 1G2 and more recent caterpillar 1M-PC, 1K, and 1N trials. I have an exam. Oil acceptability depends on oil consumption and piston deposits (top groove fill). (Top groove fill), top land heavy carbon, and heavy Based on the control of weighted deposits. Clogged piston ring Or oils that cause problems with pistons, their rings, or their liners are also rejected . Caterpillar 1N requires low sulfur content fuel (0.05% by weight), 1K is traditional Use an oil with a typical sulfur concentration (0.4% by weight).   The Mack T-7 test and its successor, the Mack T-8, Acceptable oil for engines manufactured by the Company (Mack Truck Company) It is part of a panel used to determine sex. Mac T-7 (August 31, 1984) From the date, a map named “Mac T-7: Diesel engine oil viscosity evaluation” Qu Truck Technical Service Standard Test Method No. 5GT 57) is a diesel engine Test the soot-related increase in viscosity in ginseng.   Mac T-8 ("Mac T-8 dated October 1993: Diesel engine oil viscosity evaluation The standard test method of "Mac Truck Technical Service" called "Price" It has been transformed. Because in some newer engines, Fuel injection timing to ensure that Gin meets emission requirements This is because the delay has been delayed. At the same time, the fuel has a lower sulfur content. Is formulated to alter the physical and chemical properties of soot . Designed to operate with low sulfur fuel using delayed fuel injection Some engines have very high soot-related viscosity increase, very high This results in filter pressure drop and excessive sludge buildup. Mac T-8 exam , 1010-1031 1b.-ft. 1,800 under a load of (1369.4 to 1397.8 Newton-meters) It takes 250 hours with the engine running on RPM. Throughout the exam, Measure the soot concentration, the pressure difference across the oil filter, and the kinematic viscosity of the fluid being tested. Set. Using the measured viscosity and soot concentration at a soot concentration of 3.8% by weight Interpolate the viscosity. Its viscosity is less than 11.5 cSt which is the lowest viscosity measured during the test. If not, the oil passes the test. Two if two tests are done Results should be obtained and should be less than or equal to 12.5 cSt when averaged. 3 tests If is done, the three results must be less than 13 cSt when averaged. Additional requirements include control of filter pressure differential. The Mac T-8 test is a Much more stringent than the T-7 test and requires a higher level of dispersibility in the fluid You.   Another test required for heavy duty diesel lubricants is CRCL-3 8 (ASTM D5119). This test was performed on a single cylinder laboratory gasoline engine. Done in This prevents corrosion of bearings made from copper and lead, and Designed to test the ability of lubricants to prevent sludge and varnish formation .   Heavy-duty diesel engine satisfied even off-road conditions It has to show good performance. John Deere, a farm equipment manufacturer John Deere Company is concerned about the high temperature performance of lubricants. why If so, the oil cooler is often covered with mud. John Dee Ar-6466A High Temperature Engine Oil Test Method (JDQ-78) is a heavy duty Test oil thickening due to high temperature thermal oxidation in diesel engines.   Many required to satisfy the API SH classification (and the API SG classification that precedes it) Sequence IID (ASTM STP 315h part 1), sequence Sense IIIE (ASTM D553) and Sequence VE (ASTM D5302). sequence  IID (ASTM STP 315h part 1) tests the ability of oils to prevent rust. This exam is Cold winter for short runs when condensation on the valve cover creates a corrosive environment Simulate seasonal conditions. Sequence IIIE (ASTM D553) is for oil at high temperature Measure thickening, sludge and varnish deposits, and engine wear. Sequence VE (ASTM D5302) adheres during low temperature light duty operating conditions Measure the ability of the material and the lubricant to prevent wear. The key ranking factors are the engine Includes measurements of sludge, varnish, and camshaft wear in the engine.   Another factor that complicates lubricant design is that it improves performance in one aspect. The additive or combination of additives makes the cost of the lubricant too high or another It is a well-known problem that can negatively affect the performance of.   Ripple U.S. Pat.No. 5,202,036 includes caterpillar 1G2, Mack T-7, And compositions designed to pass the CRC L-38 test. US special Xu 5,202,036 determines the amount of basicity (TNB) and source (metal ratio) of a given substance. Two parameters are used to show. Total Base Number "TNB" is used to correlate the basicity of a substance with that of potassium hydroxide. Industry standard. Values are reported as mg KOH and measured according to ASTM D2896. Is determined. Metal ratio is required to saturate the anions of organic acids. It is a calculated value for the total amount of metal present relative to the number of equivalents of metal. Metal ratio Is 1, the amount of metal present is necessary to saturate the anions of the organic acid. Amount. If the metal ratio is greater than 1, the amount needed to saturate the anions is There is much more metal. The term "overbased" is greater than one. Used to describe metal salts of organic acids with threshold metal ratios, but typically supersalts The base sulphonate salt is used in metal ratios above 2.   US Pat. No. 5,202,036 discloses certain dispersants having TNB in the range of 6 to about 15. And an alkali or alkaline earth of an organic acid having a metal ratio of at least greater than about 2 Lubricants with metal salts are described, where certain dispersants have a TN of 0.5 to 1.5. B is added, and the metal salt component is one or more magnesium salts, Murine salts contribute less than about 30% of the TNB of the composition. This patent It is not related to the tests required for Sorin fuel engines or the Mac T-8 test.   Chamberlin U.S. Pat.No. 4,941,984 describes gasoline, Intended for use in spark ignition engines fueled by Cole, or a mixture of both Described lubricants. Is this a basic magnesium salt of an organic acid? Or a basic mixture of alkaline earth metal salts of one or more organic acids (at least metal 50% is magnesium). Hydrocarbyl containing at least one hydroxyl group attached to an amine or aromatic ring With a metal salt (other than magnesium or calcium) of a bill-substituted aromatic carboxylic acid Need together. Chamberlin is "basic" when applied to magnesium salts. (basic) "is defined as:" basic magnesium salt and other Basic alkaline earth metal salts are ... excess magnesium or other alkaline earth It is called a basic salt because it contains a metal cation. Generally, basic or hyperbasic The salt has a metal ratio of about 2 to about 30 or 40. "Chambourine burns alcohol High when used in a fuel engine or an alcohol / gasoline mixed fuel engine His lubricant containing a concentration of basic (ie metal ratio ≧ 2) magnesium was Alcohol. Claiming to minimize the problems of corrosive wear and pre-ignition associated with fuel-fuel engines I have. Chamberlin also distributed his lubricant to meet the API SG classification. Insist that they can. Chamberlin's patent is a soot-related increase in viscosity And peculiar problems related to forming piston deposits in diesel engines Not something.   Using Group II Metal Hydrocarbyl Sulfonates to Achieve High TNB Another method patent, which is otherwise harmful Recognized patent is Rollin's European Patent No. 277,729 . The composition of lorin has a first (1 °) to second (2 °) ratio of about 1: 1 to about 5 :. Zinc dithiophosphate, having both first and second attributes to be 1, succinimine Do With dispersant, TNB in the finished oil is at least 8. He said succinimide The upper limit of the amount of succinimide present that is necessary to pass the friction test is It does not matter for Noh, but it is determined only by cost. Lorin has reported quite a few engine tests, but the Mac T-7 results show Not. He also found that dihydrocarbyldithio was made from a secondary alcohol. The results of the test when the metal salt of orthophosphoric acid exceeds the amount produced from the primary alcohol Not shown.   Di-diene made from certain secondary alcohols and used with certain dispersants All other patents relating to the use of zinc thiophosphate are U.S. Pat. No. 4,904,40 to Ripple. No. 1, No. 4,957,649, and No. 4,981,602.   Despite all the research done so far, In the Zell test (including Mac T-8 and Caterpillar 1N) It shows extremely good performance without sacrificing performance and is resistant to oxidation, rust, and wear. Moisture intended for use in gasoline fueled engines such as excellent resistance The demand for lubricants that provide the highest API classification requirements for lubricants depends on It exists as it is. SUMMARY OF THE INVENTION   Surprisingly, it has 0.35 to 2% by weight of sulfated ash content. And the ashless nitrogen-containing source of TBN, the ash-containing detergent with a TBN of more than 100, Magnesi Source of Um, and Dihydrocarby Having a Main or Exclusive Secondary Hydrocarbyl Group Lubricants containing ludithiophosphoric acid metal salts include CRC L-38, Sequence IID, IIIE, or Mac T-8, and track 1K and 1N without sacrificing VE performance Gives excellent performance in. The finished lubricant has 0.35 to 2% by mass of sulfated ash However, it contains a major amount of oil of lubricating viscosity, to which specific ingredients have been added. Added Ingredients are   A) Ashless nitrogen-containing dispersant, ashless nitrogen-containing dispersant viscosity modifier, oil-soluble aliphatic, o A group consisting of xyalkyl or arylalkylamines, and mixtures thereof A nitrogen-containing TBN source selected from   B) Metal salts of oil-soluble acids with TBN greater than 100,   C) A sufficient amount of mug to give at least 500 ppm (mass) of magnesium Nesium salt, and   D) at least one metal salt of dihydrocarbyl dithiophosphate, It is.   The TBN provided by the nitrogen-containing source of TBN is at least about 1.5. Oil soluble acid Of the metal salt provides at least about 40% of the total TBN of the composition. On dithiophosphate At least 50 mol% of the hydrocarbyl groups are secondary (ie, dihydrocarbyl To introduce hydrocarbyl groups into dithiophosphoric acid, a precursor of metal salts of dithiophosphoric acid At least 50 mol% of the alcohol used in is a secondary alcohol). Simple At least 60 mol% of the hydrocarbyl groups on the dithiophosphate are secondary. It is preferred that at least 75 mol% of the hydrocarbyl groups on the dithiophosphate be secondary. New Sulfated ash is the total weight percent of ash (based on the metal content of the oil), AS Determined for oils given by TM D874. Mug existing in new oil Common industry standards for measuring the amount of nesium are listed in ASTM D4951. Inductively coupled plasma atomic spectroscopy pectroscopy).   Conveniently, metal salts of oil-soluble acids with TBN greater than 100 have TBN greater than 100. It is a metal salt of oil-soluble sulfonic acid. Give at least 500 ppm magnesium The additive may be a neutral salt, but most conveniently the sulfone with a TBN greater than 100. Magnesium acid is a metal salt of an oil-soluble acid and at least 500 ppm (mass) magnesium. It is both an additive that gives a foam.   In another aspect of the invention, the lubricant described above is directly attached to nitrogen and heterocyclic nitrogen. Free of aromatic amines having at least two aromatic groups attached. The lubricant is , Free of aromatic amines having at least two aromatic groups bound directly to the nitrogen , And containing at least 0.0008 mol% hindered phenol antioxidant preferable. Hindered phenol antioxidants have steric hindrance at the hydroxyl group. It is an oil-soluble phenolic compound. In yet another aspect of the present invention, The lubricant should be at least 100 ppm (mass) boron and at least 1000 ppm (mass) phosphorus. With an additive that provides The mass ratio of boron to nitrogen is at least 0.1. You. Common industry standard methods for determining the concentrations of boron and phosphorus in lubricating oils are respectively AS TM D5185 and ASTM D4951. Detailed description   A. Lubricant   Lubricating oil is crankcase lubricating oil for spark ignition engines and compression ignition engines. Can be selected from the synthetic or natural oils used as. For convenience, the lubricating oil The raw material is about 2.5 to about 12 cSt or mm at 100 ° C.²Has a viscosity of / s and is preferably Is about 2.5 to about 9 cSt or mm²It has a viscosity of / s. If desired, with synthetic base oil Mixtures of natural base oils can be used.   B. Source of nitrogen-containing TBN   Nitrogen-containing TBN source is ashless nitrogen-containing dispersant, ashless nitrogen-containing dispersant viscosity modifier, oil Soluble aliphatic, oxyalkyl or arylalkylamines, and mixtures thereof Selected from the group consisting of objects. Nitrogen-containing ashless dispersant   In general, nitrogen-containing ashless dispersants may bind to polar particles to be dispersed. It comprises an oil-soluble polymeric hydrocarbon backbone derived by a possible nitrogen substituent. Scripture Formally, these dispersants are often attached to the polymer backbone via cross-linking groups. Includes nitrogen-containing moieties. The nitrogen-containing ashless dispersant of the present invention is a known long-chain hydrocarbon storage device. Oil-soluble salts, amines, imides, acetic acids of substituted mono- and dicarboxylic acids or their anhydrides. Mino-esters and oxazolines; thiocarbochelate derivatives of long-chain hydrocarbons Long chain aliphatic hydrocarbons with directly attached polyamines; and long chain substituted pheno The condensation of formaldehyde with polyalkylene polyamines It can be selected from the Mannich condensation products formed.   The oil-soluble polymeric hydrocarbon backbone is generally an olefin polymer, especially The required molar amount of C (ie, greater than 50 mol%) C₂~ C₁₈Olefins (eg ethi Ren, propylene, butylene, isobutylene, pentene, octene-1, styrene ), And typically C₂~ C_FiveIt is a polymer containing an olefin. Oil-soluble poly The mer hydrocarbon backbone is a homopolymer (eg, polypropylene or polyisobutene). Or a copolymer of two or more olefins (eg ethylene and propylene). Copolymers with alpha-olefins such as vinyl or butylene or two different Alpha-olefin copolymers). Other copolymers include small Of the copolymer monomer (eg 1 to 10 mol%) is C_Three~ C_{twenty two}Non-conjugated di A copolymer that is an olefin (for example, a copolymer of isobutylene and butadiene, Or ethylene, propylene, and 1,4-hexadiene or 5-ethylidene-2-norbo Runene copolymers).   One preferred group of olefin polymers is C_FourControlled by polymerization of refinery stream Polybutene, such as that which can be made, and more specifically polyisobutene (PI B) or poly-n-butene. Another preferred group of olefin polymers is Ethylene alpha-olefin (EAO) copolymer, or alpha-olefin Homopolymers or copolymers of, in each case with a high degree (eg> 30 % Of terminal vinylidene unsaturation. Therefore, the polymer has the following structure: With structure: Where P is a polymer chain and R is C₁~ C₁₈An alkyl group, typical Is methyl or ethyl. The polymer is a polymer with terminal vinylidene unsaturation. It is preferred to have at least 50% chains. This type of EAO copolymer is 1 to 50 It preferably contains ethylene by weight, preferably 5 to 45% by weight. Is more preferable. Such polymers contain more than one alpha-olefin Can, and more than one C_Three~ C_{twenty two}It can include diolefins. Another Useful is a mixture of low ethylene content EAO and high ethylene content EAO It is. EAO can be mixed or blended with various Mn PIBs, or they The ingredients derived from can be mixed or blended. European Patent Publication No. Atactic, generally having Mn of 700 to 500, as described in 490454 Propylene oligomers can also be used.   Suitable olefin polymers and copolymers include strong Lewis acid catalysts and reaction promoters. , Usually of an organoaluminum such as HCl or ethylaluminum dichloride Existence A hydrocarbon feed stream, usually C_Three~ C_FiveBy cationically polymerizing Can be manufactured. Tubular or stirred reactors can be used. Such polymerization And catalysts are described, for example, in U.S. Pat.Nos. 4,935,576 and 4,952,739. . Fixed bed catalyst systems can also be used, such as U.S. Pat.No. 4,982,045 and UK-A-2,001,662. Wear. Most commonly, polyisobutylene polymers are Raffinate Derived from the I refinery feed stream. Using traditional Ziegler-Natta polymerization , Suitable olefin polymers for use in the manufacture of dispersants and other additives. It can also be provided.   Such preferred polymers include at least one metallocene (eg, Lopentadienyl transition metal compounds) and preferably activators such as alumoxa Produced by polymerizing a suitable monomer in the presence of a catalyst system containing it can. Metallocenes are 1, 2, or more cyclopentadienyl groups (which May be substituted or unsubstituted). Metallocene also substituted Possible ligands, preferably those which are displaced by the cocatalyst, i.e. leaving groups ving group), which is usually a wide range of hydrocarbyl groups and halo groups. Selected from Gen. If desired, a cyclopentadienyl group and / or a leaving group and There may be bridges between the metal and / or the transition metal, which may be carbon, germanium, silica. It comprises one or more of a group containing elemental, phosphorus or nitrogen atoms. Transition metals are IV, V, or May be a Group VI transition metal. Such polymerizations and catalysts are described, for example, in U.S. Pat. No. 705, No. 4,937,299, No. 5,017,714, No. 5,120,867, No. 4,665,208, No. 5,1 No. 53,157, No. 5,198,401, No. 5,241,025, No. 5,057,475, No. 5,096,867, No. 5,055,438, 5,227,440, 5,064,802, U.S. Patent Application No. 992,690 (1992 Filed on Dec. 17, 2010); European Patent Publication Nos. 129,368, 520,732, 277,003 No. 277,004, No. 420,436; WO 91/04257, 93/08221, and 93/08199. Have been.   The oil-soluble polymeric hydrocarbon backbone usually has a number average molecular weight in the range of 300 to 20,000. Has (Mn). The use of the backbone is primarily for the production of dispersible components. If it is, the main chain Mn is preferably 500 to 10,000, and 700 to 5000. More preferably. Heteropolymers such as polyepoxides also produce components Useful for. Polymer with relatively low molecular weight (Mn = 500-1500) and relatively high content Both polymers of high molecular weight (Mn = 1500 to 5000 or higher) are used to make dispersants Useful. Particularly useful olefin polymers for use in dispersants are 15 It has a Mn in the range of 00 to 3000. When you want to have a viscosity adjusting effect In this case, it is desirable to use higher molecular weights, typically 2000 to 20,000 Mn. If the component is primarily intended to function as a viscosity modifier, the molecular weight can range from 20,000 It may be higher, such as Mn up to 500,000 or more. Manufacture dispersant The functionalized polymer used to do so has about 1 ends per polymer chain. It is preferable to have an end double bond.   The Mn of such polymers can be measured by several known techniques. Like that A simple method for simple measurement is by gel permeation chromatography (GPC). Which also gives information about the molecular weight distribution. W.W. Wau, J.J. Kirkland and D.D. Bly's “Modern Size Exclusion Liquid Chromatography”, J See ohn Wiley and Sons, New York, 1979.   The oil-soluble polymeric hydrocarbon backbone is functionalized to incorporate functional groups into the polymer backbone. Incorporating or incorporating functional groups as side chains from the polymer backbone Can be. The functional group is typically polar and contains P, O, S, N, halogen, or boron. It includes one or more heteroatoms such as atoms. This is an oil-soluble poly Can be attached to, or added to, the saturated hydrocarbon portion of the mer hydrocarbon backbone. Can be attached to the olefinic moiety via a cycloaddition reaction. Or the government Functional groups may be formed by the oxidation or cleavage of a small portion of the end of the polymer (eg ozonolysis). Can be incorporated into the polymer.   Useful functionalization reactions include halogenation at the olefinic bond of the polymer followed by Reaction of halogenated polymers with ethylenically unsaturated functional compounds; Halogen-free "ene" reaction with saturated functional compounds (former functionalization An example of is maleation where the polymer reacts with maleic acid or maleic anhydride. ); Reaction of the polymer with at least one phenolic group, which is a Mannich salt Allows derivatization in radical condensation); carbonyl groups at the iso or neo positions Carbon monoxide at the unsaturated point of polymers using the Koch-type reaction to introduce Reaction with hydrogen; Functionalization with polymers by radical addition using radical catalysts Reaction with substances; Reaction with thiocarboxylic acid derivatives; Air oxidation method, epoxidation, chlorination This includes the reaction of polymers by roamination or ozonolysis.   The functionalized oil-soluble polymeric hydrocarbon backbone is then further nucleophilic amine, Derived with mino-alcohols, or mixtures thereof, oil-soluble salts, amides, salts. Forms amides, amino-esters, and oxazolines. For useful amine compounds Is about 2 to 60, preferably 2 to 40 (eg, 3 to 20) total in the molecule. Carbon atoms and about 1 to 12, preferably 3 to 12, most preferably 3 to 9 Included are mono- and (preferably) polyamines having a nitrogen atom. these The amine may be hydrocarbyl amine, or may be predominantly hydrocarbyl amine. The hydrocarbyl group is another group, for example, a hydroxyl group, an alkoxy group, It may contain an amide group, a nitrile group, an imidazoline group or the like. Functionalized Amine compounds useful for derivatizing polymers include at least one amine. Only one or more additional amine groups or other reactive or polar groups You. When the functional group is carboxylic acid, carboxylic acid ester, or thiol ester When combined, it can react with amines to form amides. The preferred amine is It is an aliphatic saturated amine. Examples of suitable amine compounds are 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; diethyl Polyamines such as tritriamine, triethylenetetramine, and tetraethylenepentamine. Lyethyleneamine; and 1,2-propylenediamine, di- (1,2-propylene) tri Included but not limited to polypropylene amines such as amines.   Other useful amine compounds include 1,4-di (aminomethyl) cyclohexane Including cycloaliphatic diamines, and heterocyclic nitrogen compounds such as imidazolines It is. Such as those produced by the reaction of alkylenedihalides with ammonia Amine compounds can be used advantageously. Useful amines include polyoxyalkylene Liamine is also included. A particularly useful group of amines is U.S. Patent Nos. 4,857,217, 4,9. Polya, as disclosed in 56,107, 4,963,275, and 5,229,022. Amide and related amido-amines. U.S. Pat.No. 4,102,798, 4,113,639, 4,116,876, and Tris (hydro) described in UK 989,409. Xymethyl) aminomethane (THAM) is also useful.   Dendrimers, star amines, and comb structure amines can also be used. Similarly, the condensed amines of Steckel US Pat. No. 5,053,152 can be used. You. The functionalized polymers of the present invention are described in European Patent Publication No. 208,560 and US Pat. , 229,022 according to prior art as described therein. Such a wide range of reaction ratios are used to react with the amine compound.   A preferred group of nitrogen-containing ashless dispersants is substituted with succinic anhydride groups and Polyethyleneamine (eg, tetraethylenepentamine, pentaethylene, polyethylene Oxypropylenediamine), amino acids such as trismethylolaminomethane Alcohol, and optionally alcohols and reactive metals such as pentaerythri Polyisobutes reacted with other reactants such as toll, and combinations thereof Included are those derived from thylene.   Polyamines such as those shown in U.S. Pat.Nos. 3,275,554 and 3,565,804 are A dispersant that is directly bonded to long-chain aliphatic hydrocarbons on halogenated hydrocarbons. In which the halogen groups of are substituted with various alkylene polyamines are nitrogen-containing ashless Useful as a powder.   Another group of nitrogen-containing ashless dispersants comprises Mannich base condensation products. one Generally, these Mannich condensation products are found, for example, in U.S. Pat. As shown, about 1 mole of alkyl-substituted mono- or polyhydroxybenze The carbonyl compound (for example, formaldehyde and para Formaldehyde) and about 0.5 to 2 moles of polyalkylene polyamine Manufactured by letting Such Mannich condensation products have benzene groups Such long hydrocarbons containing long chain high molecular weight hydrocarbons (eg, 1500 or more Mn) Compounds containing elements such as polyalcohols as shown in U.S. Pat. It can react with lukenyl succinic anhydride.   Manufactured from metallocene catalysts and subsequently functionalized, derivatized, or Examples of dispersants made from functionalized and derivatized polymers are described in US Pat. 5,266,223, 5,128,056, 5,200,103, 5,225,092, 5,151,204 , US Patent Application Nos. 992,403 (filed on December 17, 1992), 992,192 (December 17, 1992) No. 070,572 (filed June 2, 1993), European Patent Publication No. 440506. , 513211 and 513157.   The functionalization, derivatization, and post-treatment described in the following patents are also preferred above. Applicable to functionalizing and / or derivatizing certain polymers: US Pat. No. 3,275, 554, 3,565,804, 3,442,808, 3,442,808, 3,087,936, and No. 3,254,025.   Nitrogen-containing dispersants are generally taught in U.S. Patents 3,087,936 and 3,254,025. Further post-treatments by various conventional post-treatments such as boration can do. This is because the acyl nitrogen dispersant is added to 1 mol of the acyl nitrogen composition. On the other hand, from about 0.1 atomic ratio of boron to 1 atomic ratio of nitrogen in the acylated nitrogen composition. Boron oxide, boron halide, boron-containing acid in an amount to provide about 20 atomic ratios of boron. And a boron compound selected from the group consisting of esters of boron-containing acids. It can be done easily with. To the total weight of borated acyl nitrogen compounds A dispersant containing about 0.05 to 2.0% by weight, for example 0.05 to 0.7% by weight of boron. Is useful. Boron, which is the dehydrated boric acid polymer (mainly (( HBO₂)_Three) Is present in the dispersant imide and diimide. It is believed to bind as an amine salt, such as the diboride metaborate.   Borination is about 0.05 to 4% by weight (based on the weight of the acyl nitrogen compound), eg For example, 1 to 3% by weight of a boron compound, preferably boric acid, which is usually a slurry. Added to the acyl nitrogen compound and added to about 135 ° C to 190 ° C, for example 140 Heat at ℃ to 170 ℃ with stirring for 1 to 5 hours, then strip with nitrogen. This can be easily done by Alternatively, the boron treatment is a dicarboxylic acid By adding boric acid to the hot reaction mixture of amines and amines while removing water. I can. Ashless nitrogen-containing dispersant Viscosity modifier   Viscosity modifiers (or viscosity index improvers) give lubricants high and low temperature serviceability. You. Viscosity modifiers that function as dispersants are also known. Generally, such dispersants Viscosity modifiers are functionalized (eg, maleic anhydride, such as those described below). Ethylene-propylene copolymers post-grafted with active monomers), The latter is a polymer derivatized with an alcohol or an amine. Dispersant viscosity modifier Is derivatized with a nitrogen-containing group, it is a nitrogen-containing TBN source contemplated by the present invention. is there. Lubricants with or without traditional viscosity modifiers and dispersant viscosity modifiers It can be formulated with or without agents. Dispersant whose lubricant contains nitrogen When a viscosity modifier is included, the contribution of TBN by the dispersant viscosity modifier is the nitrogen content of the present invention. Included in the component's TBN contribution.   Suitable compounds for use as viscosity modifiers include polyesters, generally It is a high molecular weight hydrocarbon polymer. Oil-soluble viscosity modifier polymers are generally gels. Approximately 10,000 as measured by permeation chromatography or light scattering It has a weight average molecular weight of 1,000,000 and a weight average molecular weight of 20,000 to 500,000. Is preferred.   Representative examples of suitable viscosity modifiers are polyisobutylene, ethylene and propylene. And higher alpha-olefin copolymers, polymethacrylates, poly Alkyl methacrylate, methacrylate copolymer, unsaturated dicarboxylic acid and vinyl Copolymers of nyl compounds, copolymers of styrene and acrylic esters, and Tylene / isoprene, styrene / butadiene, and isoprene / butadiene parts Partially hydrogenated copolymers, as well as butadiene and isoprene and isoprene It is a partially hydrogenated homopolymer of len / divinylbenzene.   Generally, a viscosity modifier that functions as a dispersant viscosity modifier is a Activated (eg post-grafted with an active monomer such as maleic anhydride) Ethylene-propylene copolymer), then derivatized with an alcohol or amine It is a polymerized polymer. For a description of how to make the dispersant viscosity modifier, see US Can be found in Xu 4,089,794, 4,160,739, and 4,137,185. You. Other dispersant viscosity modifiers are described in U.S. Patent Nos. 4,068,056, 4,068,058, Reaction with nitrogen compounds, as shown in 4,146,489 and 4,149,984. Or a grafted ethylene or propylene copolymer. Oil-soluble aliphatic, oxyalkyl, or arylalkylamine   It is known that alkoxylated amines improve boundary layer lubrication. these The compound may be a mono or diamine, for example                as well as Where R is H or CH_ThreeAnd R¹Is C₈~ C₂₈Saturated or unsaturated, A substituted or unsubstituted aliphatic hydrocarbyl group, preferably C_Ten~ C₂₀, The most More preferably C₁₄~ C₁₈And R²Is a linear or branched C₁~ C₆With an alkylene group Yes, preferably C₂~ C_ThreeAnd R^Three, R^Four, And R^FiveAre independently the same Or different, straight or branched C₂~ C_FiveAn alkylene group, preferably C₂ ~ C_FourAnd R⁶, R⁷, And R⁸Is independently H or CH_ThreeAnd R⁹Is linear or Branched chain C₁~ C_FiveAn alkylene group, preferably C₂~ C_ThreeX is oxygen Or sulfur, preferably oxygen; m is 0 or 1, preferably 1. Yes; and n is independently an integer from 1 to 4, preferably 1.   Conveniently, X represents oxygen, R and R¹Has a total of 18 carbon atoms, R² Is C_ThreeRepresents an alkylene group, R^ThreeAnd R^FourIs C₂Represents an alkylene group, R⁶And R⁷Is Hydrogen, m is 1, and each n is 1. Preferred amine compound Together contain from about 18 to about 30 carbon atoms in total. These amines are It can be manufactured according to the method described in Japanese Patent No. 3,456,012. X is oxygen Another method for preparing amines with m = 1 is described in US Pat. No. 4,201,684. ing. Further description of amines where X is oxygen and m = 1 is given in US Pat. Xu 3,186,946, 4,170,560, 4,231,883, 4,409,000, and 3,71 Found in No. 1,406.   The amine compound can be used as it is. However, they Boron Bromide, Boron Halide, Metaborate, Boric Acid, or Mono-, Di-, and Thor Used in the form of an adduct or reaction product with a boron compound such as rukylborate You can also. Such adducts or derivatives are, for example, the following structural formulas: Can be represented by R, R¹, R², R^Three, R^Four, X, m, and n are above Same as defined in, and R^TenIs hydrogen or an alkyl group.   Still other types of amines that can be used are polyamines and carboxylic acids or Is a reaction product with an anhydride. These compounds are described in pending U.S. Patent Application No. 031, No. 937 (filed on March 15, 1993). Briefly, polyami The hydrogen reactant contains 2 to 60 carbon atoms and 3 to 15 nitrogen atoms, and at least One nitrogen atom is present in the form of a primary amine group and at least 2 of the remaining nitrogen atoms are present. One exists in the form of primary or secondary amine groups. Examples of suitable amine compounds include diamine Ethylene triamine, triethylene tetramine, tetraethylene pentamine Una polyethyleneamine, di (1,2-propylene) triamine, di (1,3-propylene) ) Polypropylene amines such as triamines, and mixtures thereof However, it is not limited to these. Yet another suitable amine is polyoxypropylene. And polyoxyalkylenes such as polyoxyethylenetriamine Includes polyamines.   The carboxylic acid or carboxylic anhydride reactants of the above reaction products are Characterized by one of the formulas Wherein R ″ has 9 to 29 carbon atoms, preferably 11 to 23 carbon atoms A straight or branched chain, saturated or unsaturated, aliphatic hydrocarbyl group. R " Is a branched chain group, no more than 25% of the carbon atoms are in the side chain or pendant group. Not present. R ″ is preferably a straight chain. The R ″ group is mainly composed of hydrocarbyl groups. Contains a pure hydrocarbyl group. The group is characterized by the characteristics or properties of the hydrocarbyl group. If it contains non-hydrocarbyl substituents or non-carbon atoms that have little or no effect, the group is Mainly hydrocarbyl ”. For example, pure hydrocarbyl C₂₀Alkyl group And C substituted with a methoxy substituent₂₀Alkyl groups have substantially the same properties and Considered hydrocarbyl within the context of the disclosure. Carboxylic acid or carboxylic acid Most of the hydrocarbyl characteristics or properties of the general properties of the anhydrous hydrocarbyl group are Examples of substituents that do not change are ether groups (especially phenoxy, benzyloxy). , Methoxy, n-isooxy, etc., hydrocarbyloxy, especially 10 or An alkoxy group of a carbon atom in), an oxo group (for example, —O— bond in the main carbon chain) , Ester group, sulfonyl group, and sulfinyl group, but are not limited to these. Absent.   At least one of these types of amines is used at temperatures of about 120 to 250 ° C. 1 mol of the amine reactant with 1 carboxylic acid or carboxylic anhydride React at a ratio of about 2 to 10 molar equivalents of carboxylic acid or carboxylic anhydride per Can be formed by C. Oil soluble acid metal salt   The lubricant of the present invention comprises a metal salt of an oil soluble acid having a TBN of greater than 100. Of the present invention The lubricant also requires at least 500 ppm (mass) of magnesium. Oil-soluble acid The metal salt provides at least about 40% of the total TBN of the composition. Conveniently over 100 The metal salt of oil-soluble acid having TBN is a metal salt of oil-soluble sulfonic acid. Most simply Is a magnesium sulphonate having a TBN of more than 100, which is less than the metal salt of an oil-soluble acid. It is both an additive that gives at least 500 ppm magnesium.   Magnesium sulfonates with TBN greater than 100 are usually oil-soluble sulfonic acids. Completely neutralize the sulfonic acid present with a mixture of salt and alkaryl sulfonic acid Heating with an amount of magnesium compound in excess of that required for Afterwards, the dispersed carbonate complex is formed by reacting excess metal with carbon dioxide. It is manufactured by Sulfonic acids are typically used in petroleum fractionation. Or an alkyl group such as that obtained by alkylation of aromatic hydrocarbons. Obtained by sulfonation of a substituted aromatic hydrocarbon. Examples are benzene, toluene , Xylene, naphthalene, diphenyl, or chlorobenzene, chlorotoluene, And obtained by alkylation of their halogen derivatives such as chloronaphthalene Included. Alkylation involves catalysis and about 3 to more than 30 carbon atoms. It can be carried out in the presence of an alkylating agent having. For example, haloparaffin, Olefin obtained by dehydrogenation of raffin, or ethylene or propylene All polyolefins produced from are suitable. Alkaryl sulfonate is Usually from about 9 to about 70 or more carbons per alkyl-substituted aromatic moiety. It has elementary atoms, preferably about 16 to about 50 carbon atoms.   Oil-soluble sulfonate or alkaryl sulfonic acid is magnesium oxide , Hydroxide, alkoxide, carbonate, carboxylate, sulfide, hydrosulf It can be neutralized with chloride, nitrate, borate, and ether. Where to find the final product Consider the desired TBN, but typically about 100 to 220 wt% (preferably at least 1 An amount of magnesium compound of 25% by weight) is selected.   EP 312313, 13807, 13808, 15351, 312315, WO 92/20694 There are various known methods for producing superbased alkaryl magnesium sulfonate. is there.   The preferred overbased magnesium sulfonate additive is in the range of about 300 to about 440. TBN and about 25 to about 3 based on the total weight of the additive system dispersed in the mineral lubricating oil. Alkyl aromatic sulphates having a magnesium sulphonate content in the range of 2% by weight It is magnesium fonate. The metal ratio of this preferred material is greater than 10, The pattern is about 15.   Others that can be used in combination with the above-mentioned overbased magnesium salts of sulfonic acids The dispersants for oils include oil-soluble neutral or overbased sulfonates (overbased sulfonate (Other than gnesium), phenates, sulfurized phenates, thiophosphonates, Licylate and naphthenate, and metal, especially alkali metal or alkaline earth Metals such as sodium, potassium, lithium, calcium, and magnesium And other oil-soluble carboxylic acid salts thereof. The most commonly used metals are , Calcium and magnesium, mixtures of calcium and magnesium, and calcium It is a mixture of sium, magnesium, or both with sodium. Overbasing The cleaning agent acts as a cleaning agent and acid neutralizer, thereby reducing wear and corrosion. And extend the life of the engine. Traditional metal-based detergents include neutral and basic sulphates. Calcium phosphate, neutral and basic calcium phenates and sulfurized phenates, And neutral magnesium sulfonate. D. Dihydrocarbyl dithiophosphoric acid metal salt   Metal salts of dihydrocarbyl dithiophosphate are often used as antiwear and antioxidant agents. used. The metal is an alkali metal or alkaline earth metal, or aluminum, It may be lead, tin, molybdenum, manganese, nickel or copper. Zinc salt in lubricating oil At 0.1 to 10% by weight based on the total weight of the lubricating oil composition, preferably 0.2 to Most commonly used in an amount of 2% by weight. They are communicated according to known techniques. Usually one or more alcohols or phenols and P₂S_FiveThe reaction with Drocarbyl dithiophosphoric acid (DDPA) is formed and then the formed DDPA is treated with a zinc compound. It can be produced by neutralization. Zinc dihydrocarbyl dithiophosphate is an alcohol Can be made from a DDPA mixture. Or multiple species of dihydric Zinc locarbyl dithiophosphate can be prepared and then mixed.   Therefore, the dithiophosphoric acid containing a secondary hydrocarbyl group used in the present invention is , Can be produced by reacting a mixture of primary alcohol and secondary alcohol You. Alternatively, the hydrocarbyl group on one side is completely secondary and the hydrocarbyl group on the other side is It is possible to produce several dithiophosphoric acids in which the locarbyl group is completely first. Although any basic or neutral zinc compound could be used to make the zinc salt, The oxides, hydroxides, and carbonates are most commonly used. Commercial additives are medium Since an excess amount of basic zinc compound is used during the summing reaction, it is necessary to include excess zinc. There are many.   The preferred zinc dihydrocarbyl dithiophosphates useful in the present invention are dihydrocarbyl dithiophosphates. A soluble salt of carbyl dithiophosphoric acid, having the formula: Can be represented by the formula, where R and R ′ are the same or different and are 1 to 18 An alkyl group, preferably a hydrocarbyl group containing 2 to 12 carbon atoms, Such as alkenyl, aryl, arylalkyl, alkaryl, and cycloaliphatic groups Including a group. Particularly preferred R and R'groups are those having 2 to 8 carbon atoms. It is a kill group. Thus, such groups are for example ethyl, n-propyl, i-pro Pill, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n- Octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, bu Tylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl It is. To obtain oil solubility, the total number of carbon atoms in dithiophosphoric acid (ie, R and R ') is generally about 5 or more. Therefore, zinc dihydrocarbyl dithiophosphate is Zinc alkyldithiophosphate can be included. Hydrocarbyl group on dithiophosphoric acid At least 50 (mol)% of the alcohol used to introduce is a secondary alcohol It is. Higher percentages of secondary alcohols are preferred and especially high nitrogen Required in the elementary system. Therefore, it is used to introduce hydrocarbyl groups The alcohol may be 60 to 75 mol% second. Hydrocarbyl group is more than 90 mol% Most preferably, it is second. E. FIG. Other ingredients   Additional additives are generally incorporated into the compositions of this invention. Of such additives Examples are additional dispersants, antioxidants, antiwear agents, friction modifiers. , Rust inhibitors, defoamers, demulsifiers, and pour point depressants.   An additional dispersant, ie a nitrogen-free dispersant, can be used. Containing these nitrogens The dispersant is a mono-functional dispersion of the functionalized oil-soluble polymeric hydrocarbon backbone described above. And hydroxyl compounds such as polyhydric alcohols, or phenols or naphtho It may be an ester prepared by reacting with an aromatic compound such as silane. For example, ethylene glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, dipropylene glycol, and alkylene groups are 2 To other polyhydric alcohols, such as other alkylene glycols having from about 8 carbon atoms. Call is preferred. Other useful polyhydric alcohols include glycerol and glyceride. Roll monooleate, glycerol monostearate, glycerol molybdate Nomethyl ethyl ether, pentaerythritol, dipentaerythritol, and And mixtures thereof.   Ester dispersants include allyl alcohol, cinnamyl alcohol, propargyl (propargyl) alcohol, 1-cyclohexan-3-ol, and oleyl alcohol It can also be derived from unsaturated alcohols such as Ashless dispersion without nitrogen Other groups of alcohols from which agents can be produced include, for example, oxy-alcohols. Included are xylene, ether-alcohols including oxy-arylene. They are An ether-alcohol having up to about 150 oxy-alkylene groups, , Alkylene groups are exemplified by those containing from 1 to about 8 carbon atoms.   Ester dispersants are diesters or acid esters of succinic acid, that is, partially Esterified succinic acid, as well as partially esterified polyhydric alcohols or Is a phenol, that is, an ester having an alcohol or a hydroxyl group of phenol. It may be tel.   Ester dispersants may be any of the known agents such as those shown in U.S. Patent 3,381,022. It can be manufactured by one of several methods. Ester dispersant It can also be borated in the same manner as the above-mentioned nitrogen-containing dispersant.   Antioxidants reduce the tendency of mineral oils to deteriorate during use. Deterioration of mineral oil is due to metal Oxidation products such as sludge and varnish deposits on the surface or of viscosity You can prove it by increasing. Such antioxidants include hindered phenols, Preferably C_Five~ C₁₂Alkylphenol Thioesters with Alkyl Side Chains Alkaline earth metal salts, calcium nonylphenol sulfide, ashless oil soluble flux Phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphites, Thiocarbamic acid metal salts, oil soluble as described in U.S. Patent No. 4,867,890 Copper compounds and molybdenum-containing compounds are included. Examples of molybdenum compounds , Molybdenum salts of inorganic or organic acids (see, for example, U.S. Pat.No. 4,705,641). And), especially monocarboxylic acids having 1 to 50, preferably 8 to 18 carbon atoms Molybdenum salts of acids such as molybdenum octoate (2-ethylhexanoate ), Naphthenates, or stearates; disclosed in European Patent Publication No. 404 650. -Based molybdenum containing complexes such as those described above; molybdenum dithiocarbamate and And molybdenum dithiophosphate; disclosed in US Pat. Nos. 4,995,996 and 4,996,719. -Soluble molybdenum xanthates and thioxanthates And oil-soluble molybdenum-containing and sulfur-containing complexes.   In one aspect of the invention, the lubricant is at least 0.0008 mol% hindered pheno. Including antioxidants. Generally, hindered phenols contain one or both It is an oil-soluble phenol that is substituted at the G position. Suitable compounds include 2,6-di-ter t-alkylphenols (eg 2,6-di-t-butylphenol, 2,4,6-tri-t-butyl Tylphenol, 2-t-butylphenol, 4-alkyl-2,6-t-butylphenol , 2,6-diisopropylphenol, and 2,6-dimethyl-4-t-butylphenol) Monovalent mononuclear phenols such as Other suitable hindered fenoes Alkylene-bridged hindered phenol (4,4-methylenebis (6-t-butyl) -o-cresol), 4,4'-methylenebis (2-t-amyl-o-cresol), and 2,2 Polyvalent polynuclear pheno such as ′ -methylenebis (2,6-di-t-butylphenol)) Included. Hindered phenols can be borated or sulfurized. Preferred Fresh hindered phenols have good oil solubility and relatively low volatility.   Friction modifiers can be included to improve fuel economy. To add nitrogen TBN In addition to the above oil-soluble aliphatic, oxyalkyl, or arylalkylamines of , Other friction modifiers are also known. Among them, carboxylic acids or carboxylic acids There is an ester formed by reacting the anhydride with an alkanol . Other conventional friction modifiers generally have a polar covalent bond to a lipophilic hydrocarbon chain. It consists of end groups (eg carboxyl or hydroxyl). Carboxylic acid and Esters of rubonic anhydride and alkanols are described in U.S. Pat.No. 4,702,850. ing. Examples of other conventional friction modifiers include M.I. Belzer's “Journal of Tribolog y "(1992), Vol. 14, pp. 675-682, and M. Belzer and S. Jahanmir," Lubrica ". -tion Science "(1988), Vol. 1, pp. 3-26.   Nonionic polyoxyalkylene polyols and their esters, polyoxy Selected from the group consisting of sialkylene phenols and anionic alkyl sulfonic acids. Any selected rust inhibitor can be used. When the formulation of the invention is used, this These rust inhibitors are generally not needed.   Corrosion inhibitors for copper and lead bearings can be used, but in the formulation of the present invention Is generally not needed. Typically, such compounds have from 5 to 50 carbons Thiadiazole polysulfides having atoms, their derivatives and polymers You. Described in U.S. Pat.Nos. 2,719,125, 2,719,126, and 3,087,932 Derivatives of 1,3,4-thiadiazole, such as those present, are common. Other similarities The substances of U.S. Pat.Nos. 3,821,236, 3,904,537, 4,097,387 and 4,107,0 59, 4,136,043, 4,188,299, and 4,193,882. Other additives, such as those described in British Patent Specification No. 1,560,830 Thiadiazole thio and polythiosulfenamides. Benzotriazo The polyol derivatives also fall into this group of additives. These compounds are incorporated into the lubricant composition. If present, it is preferably present in an amount not exceeding 0.2% by weight of the active ingredient.   A small amount of demulsifier component can also be used. Preferred demulsifier components are described in EP 330,522 Have been. Demulsifier component reacts bis-epoxide with polyhydric alcohol Obtained by reacting the alkylene oxide with the adduct obtained by Can be Demulsifiers must be used at levels not exceeding 0.1% by weight of active ingredient No. The use amount of the active ingredient of 0.001 to 0.05 mass% is simple.   Pour point depressants (also known as lube oil viscosity modifiers) are fluids that flow It is possible to lower the minimum temperature. Such additives are known. Low fluid Typical of these additives which improve the warm fluidity are C₈~ C₁₈Dialkylf Malate / vinyl acetate copolymer and polyalkylmethacrylate .   Suppression of foaming is achieved by defoaming agents of the polysiloxane type, such as silicone oil or polydiethylene. This can be done with many compounds, including methyl siloxane.   Some of the additives described above can provide multiple benefits. For example, alone Additives can act as dispersants and antioxidants. This method is well known Yes, no further detailed explanation required. F. Additives that can adversely affect some lubricant performance   Several known classes of additives have been found in universal crankcase lubricants. Often used. Aromatic having at least two aromatic groups directly bonded to nitrogen Amines are often used because of their antioxidant properties. Few of these substances Although it can be used in amounts, preferred embodiments of the present invention do not include these compounds. . These aromatic amines adversely affect soot-induced increase in viscosity. There was found. It is preferable to use a very small amount of these and other components of the composition. More preferably, it is not contained at all, except in the amount provided as impurities.   Typical oils having at least two aromatic groups attached directly to one amine nitrogen Soluble aromatic amines have 6 to 16 carbon atoms. 2 or more of these amines Of aromatic groups. Have a total of at least 3 aromatic groups and 2 Aromatic groups of covalent bonds or atoms or groups (eg oxygen or sulfur atoms, or Is -CO-, -SO₂-Or an alkylene group) and two are one Compounds that are directly bonded to the amine nitrogen also have fewer aromatic groups that are directly bonded to the nitrogen. Is also considered to be an aromatic amine having two. The aromatic ring is typically an alkyl group. Group, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, Substituted by one or more substituents selected from droxy and nitro groups You. These compounds must be minimized or eliminated altogether. why If so, these compounds show a dramatic increase in soot-related viscosity on Mac T-8. It has been found to affect the. Aromatic directly bonded to one amine nitrogen The amount of such oil-soluble aromatic amines having at least two groups is 0.2% by weight. It is preferable not to exceed the amount of active ingredient. G. FIG. blend   When the lubricant composition comprises one or more of the above-mentioned additives, each additive generally Is blended with the base oil in an amount that can provide the desired function of. Crankcase lubrication Representative effective amounts of such additives when used in the formulation are shown below. Indication All values given are stated as% by weight of active ingredient.   1. Nitrogen-containing ashless in multigrade oils with dispersant viscosity modifiers Dispersants can be used at much lower treat rates. In this case, add the dispersant viscosity modifier. It acts as a source of additional nitrogen-containing TBN. At least one pair of researchers (Papke et al. No. 5,294,354) is a specific dispersant viscosity control in which the amount of conventional ashless dispersant used is 0. Formulations containing formulating agents are reported. In that case, the dispersant viscosity modifier is nitrogen-containing TBN. Acts as a source.   2. Viscosity modifiers are used only in multigrade oils.   The amount of ashless dispersant is determined in part by the TBN requirements of the present invention, and , To qualify test fluids without unnecessarily increasing the cost of finished lubricants Location without degrading performance in one or more of many relevant areas It is also determined by the requirements to achieve the desired dispersibility. Useful compositions are dispersed Balance many properties, including wettability, detergency, anti-oxidation, and anti-wear properties. I have to. To improve one of these properties in many instances In addition, increasing the concentration of additives degrades one or more of the other properties. This meaning In, the formulator's challenge is to maintain each cost while maintaining an acceptable cost. The goal is to define a feasible area for the players.   Modulating the contribution of TBN from nitrogen-containing species can affect the soot-related increase in viscosity. It turned out. Substantially increase the amount of polymer using various compounding techniques Without nitrogen source of TBN (ie nitrogen containing ashless dispersant, nitrogen containing viscosity modifier , And all oil-soluble aliphatic, oxyalkyl or arylalkyl groups present. A finished oil from Min) can achieve a contribution of at least 1.5 to the total TBN You. TBN, a traditional dispersant, is used to aminate functionalized polymer backbones. The type and amount of amines (amine content, branching, and size) that are consumed Can be increased by Alternatively, the polymer backbone is more functional. It can be functionalized with groups. Simply put a conventional high molecular weight dispersant into a conventional low molecular weight Blended with the dispersant to increase the total amount of TBN to the dispersant polymer backbone. Can be   When determining the amount and type of nitrogen that should be present in the ashless dispersant, the amount of nitrogen in the lubricant should be determined. Care must be taken against other sources of nitrogen-containing TBN. For example, the viscosity of the dispersant Modifiers are often derived using nitrogen. Given by the nitrogen-containing source of TBN All nitrogen-containing dispersants viscosity modifiers to lubricant TBN when calculating TBN Include the contribution of.   Other nitrogen-containing TBN sources that can significantly increase TBN from nitrogen-containing species Is an oil-soluble aliphatic, oxyalkyl, or arylalkylamine. Comparison A small amount of these compounds can be used as a lubricant without affecting other performance of the dispersant. The TBN of can be changed. Surprisingly, this change in TBN is associated with soot The increase in viscosity is suppressed.   Nitrogen-containing ashless dispersant, nitrogen-containing viscosity modifier, and oil-soluble aliphatic, oxyalkoxy Or the total amount of TBN provided by the arylalkylamine is at least 1 It should be .5. Conveniently, the TBN provided by the nitrogen-containing additive is 1.5 To 2.8. Their contribution to TBN preferably does not exceed 2.2.   Controlling the amount of TBN by the ash-containing salts of oil-soluble acids is another feature of the invention. It is a sign. Conveniently, use overbased magnesium sulfonate to remove all lubricant It can contribute to at least 40%, preferably at least 60% of the TBN. Also, the lubricant should be at least 500 ppm (mass) magnesium (overbased sulfo). (With magnesium oxide or other magnesium detergent) I have to. These concentrations of magnesium can be found in Sequence IID (ASTM STP 315hpa rt 1) gives excellent performance.   The use of a second metal salt of hydrocarbyl dithiophosphate is also important. Switch to metal salt Of the alcohol used to introduce the hydrocarbyl group into the dithiophosphoric acid At least 50 mol% should be secondary. Secondary alcohol percentage The larger the size, the more preferable it is, and it is required especially in a high nitrogen system. Therefore The alcohol used to introduce the hydrocarbyl group is 60 to 75 mol% Two is fine. Most preferably more than 90 mole% of the hydrocarbyl groups are secondary . The dithiophosphoric acid metal salt having the second characteristic is sequence VE (ASTM D5302) and GM6. Gives better wear control in tests such as the 2L test. Soot-related stickiness The high-concentration nitrogen-containing TBN source required in the present invention to suppress the increase in wear And adversely affects the corrosion prevention performance. High TBN harmful due to nitrogen-containing components The effect is that by using a high concentration of the metal dithiophosphate having the second characteristic, And the use of boron to control bearing corrosion.   In a preferred embodiment, the lubricant has fewer aromatic groups directly attached to the nitrogen. It does not contain aromatic amines having at least two. These aromatic amines, especially alkynes Fluorinated diphenylamine was found to adversely affect the soot-related increase in viscosity. Revealed. These ingredients have been widely used in the past due to their excellent antioxidant properties The TBN level due to the contribution of nitrogen-containing components Can approach the minimum value of 1.5, thereby eliminating the harmful effects associated with excess nitrogen. Can be minimized. Lubricants contain few aromatic groups directly bonded to nitrogen. Contain less than 0.2% by weight of the active ingredient of these aromatic amines with at least two Preferably not.   A particularly good inhibition of oil thickening is obtained by the composition of the present invention being alkyl substituted diphenylamine. It is obtained when it contains no hindered phenol and contains hindered phenol. Due to nitrogen-containing source The upcoming TBN suppresses soot-related oil thickening, while dithiophosphoric acid metal salts and hinders Dephenol suppresses the thickening of oil due to thermal oxidation. Surprisingly, Jiffeny Ruamine exacerbates soot-induced thickening, but hindered phenols Exacerbates soot-induced thickening (including alkylene-bridged bisphenols) Do not let.   Yet another embodiment of the present invention requires one or more boron-containing additives, Therefore, the lubricant contains at least 100 ppm (mass) of boron. Conveniently, 1 lubricant Contains 80 ppm (mass) boron. Boron corrodes bearings made from copper and lead Help control. The high concentration of nitrogen and magnesium required in the present invention Corrosion of these copper / lead bearings can be adversely affected. Conveniently, The mass ratio of elemental to nitrogen is greater than 0.1. Those skilled in the art will appreciate the various methods of introducing boron. Is known. For example, dispersant or oil-soluble aliphatic oxyalkyl, or aryl The alkyl amine can be borated as described above. Or Small United States As described in US Pat. No. 4,629,576 and Liston US Pat. The oil-soluble polyol can be borated.   Yet another embodiment is such that the lubricant comprises at least 1000 ppm (mass) phosphorus. Requires one or more phosphorus-containing compounds. Conveniently, the lubricant is 1100 ppm (mass) Contains phosphorus. Phosphorus can be present in the metal salt of dithiophosphoric acid. Alternatively, phosphorus is a phosphorus-containing oxidation Phosphorylating dispersants or by using inhibitors or antiwear components Can be introduced by These high concentrations of phosphorus inhibit corrosion in CRC L-38 To help you. For convenience, the phosphorus concentration should not exceed 1500 ppm (mass). Phosphorus Preferably the degree does not exceed 1200 ppm (mass).   Each component can be incorporated into the base oil by any convenient method. Therefore, By dispersing or dissolving each of the minutes in the oil at the level of the desired concentration It can be added directly to the oil. Such blending is done at ambient or elevated temperature be able to.   Blend all additives except viscosity modifiers and pour point depressants into concentrates It is preferred to blend the concentrate into the base stock to produce the finished lubricant. That The use of such concentrates is conventional. In general, concentrates should be determined beforehand. In the final composition when combined with a controlled amount of base lubricant. It is formulated to contain the additives in the appropriate amounts to give the desired concentrations.   Concentrates are preferably made according to the method described in U.S. Patent No. 4,938,880. Good. This patent describes an ashless dispersant preblended at a temperature of at least about 100 ° C. And producing a premix of a metallic detergent. afterwards Cool the premix to at least 85 ° C and add the other ingredients. That Advantageously, such concentrates contain the following additives:   1. Nitrogen-containing ashless in multigrade oils with dispersant viscosity modifiers Dispersants can be used in much lower amounts. In this case, add a dispersant viscosity modifier Acts as a source of nitrogen-containing TBN. At least one set of researchers (US patents from Papke et al. No. 5,294,354) is a specific dispersant viscosity adjustment in which the amount of conventional ashless dispersant used is zero. A formulation containing an agent is reported. In that case, the dispersant viscosity modifier is a nitrogen-containing TBN source. Acts as.   The final composition is 2 to 15% by weight, preferably 5 to 10% by weight, typically 7 to 8 wt% additive package can be used with the balance being base oil. Good The preferred concentrate is A) ashless nitrogen-containing dispersant, oil-soluble aliphatic, oxyalkyl, or A nitrogen-containing atom selected from the group consisting of arylalkylamines, and mixtures thereof. Sources of TBN, B) metal salts of oil-soluble acids with TBN greater than 100, C) at least 3100 ppm Magnesium salt in a concentration that gives (mass) magnesium, and D) at least one kind Of dihydrocarbyl dithiophosphoric acid metal salt. At least about 10 nitrogen-containing TBN sources TBN of the concentrate is provided, and the metal salt of the oil-soluble acid provides at least about 40% of the total TBN of the concentrate. And at least 50 mol% of the hydrocarbyl groups on the metal dithiophosphate are It is two.   The invention will be further described by reference to the following examples. In the examples Unless otherwise specified, the additive amounts are reported as% by weight of active ingredient. Have been. Example 1   The following ingredients are added to the base material with lubricating viscosity to add 30 grade crankcase. A lubricant was prepared: borated polyisobutenyl succinimide dispersant (PIB Mn = 22 50, PIBSA: amine = 1.5: 1, borinated), magnesium petroleum sulfonate metal-based cleaning Inhibitor (400 TBN), additional oil-soluble organic acid metal salt detergent inhibitor, antioxidant Agents, zinc dihydrocarbyl dithiophosphate, amine friction modifiers, defoamers, demulsifiers, And pour point depressants. Blend the same additive and olefin copolymer viscosity modifier Manufactured the SAE 15W-40 multi-grade crankcase lubricant. Both finished lubrication The agent is     Boron 200 ppm     Magnesium 1120 ppm     Phosphorus 1120 ppm     TBN 7.95     TBN 1.8 from nitrogen containing sources     TBN 4.9 from magnesium sulfonate     % Of TBN from magnesium sulfonate 61.9     Molar% of secondary hydrocarbyl groups in ZDDP 90.9     Ratio of boron to nitrogen (mass ratio) 0.2   Testing both lubricants gave the results shown in Table I. These lubricants are Excellent rust resistance, soot handling control, suppression of diesel deposits Control, bearing corrosion resistance, and wear resistance, and suppresses oxidation (Sequence II Performance in other important areas such as IE) and sludge in gasoline engines And kept the protection from varnish (sequence VE). Example 2   To test the effect of varying the contribution to TBN from nitrogen-containing sources Brake the crankcase lubricant by adding the following ingredients to the base material: Bonded: Borated Polyisobutenyl Succinimide Dispersant, Petroleum Sulfonate Mag Nesium metal-based cleaning agent inhibitor (400 TBN), cleaning of metal salts of additional oil-soluble organic acids Agent inhibitor, defoamer, demulsifier, olefin copolymer viscosity modifier, and pour point depressant laxative. This reference lubricant was added to various additional nitrogen-containing TBN sources and dihydrides shown in Table II. Zinc locarbyl dithiophosphate was added. Mac T-8 test for each lubricant went. Example 3   Alkylated diphenyls as shown by test fluids on Mac T-8 It has been found that amines increase the soot-related increase in viscosity. The lubricant is Aromatic amines with two aromatic groups attached directly to the nitrogen of the min It should not be included (that is, the amount used should not exceed 0.2% by weight of the active ingredient) and should not be included at all. It is preferable. To show this effect, the following ingredients should be added to the base material. Blended two crankcase lubricants with and: Borated polyisobute Nylsuccinimide dispersant, magnesium petroleum sulfonate metal detergent inhibitor ( 400 TBN), Detergent Inhibitor of Additional Oil Soluble Organic Acid Metal Salts, Dihydrocarbyldiene Zinc thiophosphate, defoamer, demulsifier, olefin copolymer viscosity modifier, and flow Point depressant. Two types of oils, only one of which contains mixed nonyldiphenylamine Was tested in the Mack T-8 test. Of alkylated diphenylamine amount and test The results are shown in Table III. Example 4   Borated polyisobutenyl succinimide dispersant, magnesium petroleum sulfonate Metal-based detergent inhibitor (400 TBN), additional oil-soluble organic acid metal salt detergent inhibitor Two kinds of zinc dihydrocarbyl dithiophosphate, mixed nonyldiphenylamine, thi Odiazole corrosion inhibitors, antioxidants, defoamers, demulsifiers, and pour point depressants Including Nitrogen functionalized as shown by the following tests performed on High molecular weight viscosity index improvers to reduce soot-induced viscosity increase Can be. In one lubricant, the viscosity modifier is a conventional olefin copolymer Viscosity modifier, small amount of nitrogen functionalized polymethylmethacrylate (PMA) In the other lubricant, the only viscosity modifier included is a nitrogen-functionalized polymethy It was methacrylic acid. Find out from the results of the Mac T-8 shown in Table IV Thus, the dispersant viscosity modifier reduced the soot-induced increase in viscosity. Example 5   Lowest concentration of magnesium that can be provided by overbased magnesium sulfonate Is required. Boronated polyisobutenyl succinimide dispersant as base material , Magnesium petroleum sulfonate metal-based detergent inhibitor (400 TBN), with additional oil solubility Detergents for metal salts of organic acids, antioxidants, zinc dihydrocarbyl dithiophosphate ( ZDDP) (90.9 mol% secondary hydrocarbyl groups), defoamers, demulsifiers, olefins By adding a copolymer viscosity modifier and a pour point depressant, two types of black are added. Rank case lubricant was blended. Ultrabasic Petroleum Sulfonate Mag Included These two types of moisturizers differ only in the amount of nesium metal detergent inhibitor (400 TBN). Lubricants were tested in Sequence IID (ASTM STP 315h part 1). Details of the composition Table V shows the details and the test results. Example 6   Boron suppresses the attack of nitrogen on bearings made of copper and lead. High Boron is especially needed in systems containing high concentrations of nitrogen. As a base material, Sobutenyl succinimide dispersant, magnesium petroleum sulfonate metal-based detergent prohibited Stopper (400 TBN), additional oil-soluble organic acid metal salt cleaner inhibitor, antioxidant, Dihydrocarbyl zinc dithiophosphate (90.9 mol% secondary hydrocarbyl groups), antifoam Agents, demulsifiers, friction modifiers, olefin copolymer viscosity modifiers, and pour point depressants Blends two 5W-30 crankcase lubricants by adding a lubricant Was. One contains a borated dispersant and the other contains a non-borated dispersant These two lubricants differ only in the points tested in CRC L-38 (ASTM D5119) did. Example 7   In this example, the mass ratio of boron to nitrogen in the final composition should be set to 0.1 or more. Indicate the need for. Mixing a polyisobutenyl succinimide dispersant with the base material Oil, magnesium petroleum sulfonate metal detergent inhibitor (400 TBN), additional oil soluble Detergents, Antioxidants, Dihydrocarbyldithiophosphates for Metal Salts of Organic Organic Acids Lead (90.9 mol% secondary hydrocarbyl groups), defoamers, demulsifiers, friction modifiers, By adding a reffin copolymer viscosity modifier, and a pour point depressant, 2 Blended with different types of crankcase lubricants. Mixture of dispersants and dihydrocarbi These two lubricants differing only in the amount of zinc ludithiophosphate were used in CRC L-38 (ASTM D 5119). Adjustments in the mixture of dispersants include polysuccinyl groups on the It affected the amount of isobutenyl substituents and Mn, as well as the amounts of nitrogen and boron. Details of the composition The details and test results are shown in Table VII. Example 8   Use ZDDP or a mixture of ZDDPs having a secondary hydrocarbyl group predominantly or exclusively The need to do this is explained by the following data from an experimental cylinder head rig. I will tell. As a base material, polyisobutenyl succinimide dispersant, petroleum sulfone Magnesium acid metal detergent inhibitor (400 TBN), antioxidant, 1 or 2 types Zinc dihydrocarbyl dithiophosphate, antifoaming agent, demulsifier, olefin copolymer viscosity 3 types of crankcases by adding a degree adjusting agent and a pour point depressant A lubricant was produced. The rig used was Nuneat (Warks), Nuneat. on) Motor Industries Research Association (Motors Indus Cam and Tappet Rig (developed and supplied by the Try Reaserch Association) tappet rig). This is a 30 mm circular cam of induction heated and cooled cast iron. Including, the cam moves on the 12.5 mm eccentric shaft against the EN 32b tappet and G has a radius of 2 m at the contact surface. The load is variable resistance spring Is added. Lubrication is by a high pressure jet from a heated reservoir. Adjust the flow rate to 150 ml / min. Wear tests are performed according to the following protocol. speed 1500 rpm for a period of 20 minutes with a load of 20 kgm (operation), and then with a load of 60 kgm for 60 minutes. Jun Sliding performance was measured in terms of follower wear. This is a follow-up before the test The Vickers hardness indentation formed at the center of the Determined by the decrease in size. All test parts are standard and must be Supplied by the manufacturer of the device. The tests carried out on the above test oils are 65 Performed at an oil temperature of ° C. The results are shown in Table VIII. Hydro existing on ZDDP Three lubricants that differ only in carbyl-based mixtures give very different wear resistance. I got it. Lubricants in which the hydrocarbyl groups present on the ZDDP are primarily or exclusively secondary Gave excellent wear resistance. Example 9   The use of zinc dihydrocarbyl dithiophosphate containing predominantly a secondary hydrocarbyl group is Required to achieve satisfactory wear resistance in Sequence VE (ASTM D5302). is there. Systems containing high concentrations of nitrogen can compromise the wear protection of the fluid. main Using zinc dihydrocarbyl dithiophosphate containing a secondary hydrocarbyl group in In order to show the value of the base material, polyisobutenyl succinimide dispersant, Magnesium Petroleum Sulfonate Metallic Detergent Inhibitor (400 TBN), Antioxidant, 1 Or two kinds of zinc dihydrocarbyl dithiophosphate, defoaming agent, demulsifier, olefin By adding a copolymer viscosity modifier and a pour point depressant, three types of Rank case lubricants were manufactured. Multiple nitrogen-containing components (one is amine friction modifier) The amount of TBN from (including) and the mole percent of secondary hydrocarbyl groups on ZDDP Three different lubricants were tested in Sequence VE.   Sequential VE (ASTM D5302) tests should be performed when using a system containing high concentrations of nitrogen. In order to suppress wear, the secondary hydrocarbyl group is therefore mainly or exclusively It is necessary to use a ZDDP or a mixture of ZDDPs that have. Example 10   Amine with at least two aromatic groups attached directly to the nitrogen results from soot Must be removed as it adversely affects the thickening of the oil, but due to thermal oxidation An antioxidant is necessary to suppress thickening of oil. Historically, it contained no phosphorus The antioxidant concentration provided by zinc dihydrocarbyl dithiophosphate To an acceptable level, often less than 1500 ppm in the final lubricant, preferably 12 It has been used to stay below 00 ppm (mass). Yoshi directly bonded to nitrogen Aromatic amines having at least two aromatic groups, eg alkyl-substituted diphenyl groups Min was the particularly preferred phosphorus-free antioxidant. Surprisingly, Hinda Dephenolic antioxidants adversely affect the thickening of oil caused by soot First of all, it can be used instead of diphenylamine. TB containing high levels of nitrogen The advantage of the present invention of using an N source and hindered phenol is John Deere  Deere) 6466A test. This test increases the viscosity due to thermal oxidation Combines the thickening of oil caused by soot.   To demonstrate the efficacy of hindered phenols in the Sequence IIIE study, 4,4 Two types of molybdenum differing only in the amount of ′ -methylene-bis-2,6-di-tert-butylphenol. Lubricants were tested in the Sequence IIIE test. The results of viscosity increase are shown in Table X. .   To show that hindered phenols do not adversely affect the Mac T-8 test , All the same 2 except one contains a hindered phenol antioxidant A variety of lubricants were tested in the T-8 test. Lubricant containing hindered phenol Within the accuracy of the test, from a lubricant that does not contain hindered phenol. Indistinguishable test results were given (at 3.8 wt.% Soot, a viscosity of 24.84 vs. 22.57). Increase).   The surprising effect of the present invention to suppress oil thickening caused by soot and thermal oxidation is di- Found in the Jon Dear JD 6466A exam. This test is for oxidation, abrasion and 6 cylinders, 226 hp to evaluate the ability of lubricants to control kimono and oil consumption Use the engine of. In Table X (a), the SAE 15W40 lubricant according to the invention is mixed in Conventional SAE with synthetic nonyldiphenylamine but no hindered phenol Compared to the 15W40 composition. The lubricant of the present invention has excellent performance in all aspects. However, conventional lubricants fail to meet the viscosity goals of the test.

[Procedure of Amendment] Article 184-8 of the Patent Act [Submission date] June 28, 1996 [Correction contents] Amendments to the translation of the description, page 5, line 6 to page 6, line 16   Chamberlin U.S. Pat.No. 4,941,984 describes gasoline, Intended for use in spark ignition engines fueled by Cole, or a mixture of both Described lubricants. Is this a basic magnesium salt of an organic acid? Or a basic mixture of alkaline earth metal salts of one or more organic acids (at least metal 50% is magnesium). Hydrocarbyl containing at least one hydroxyl group attached to an amine or aromatic ring With a metal salt (other than magnesium or calcium) of a bill-substituted aromatic carboxylic acid Need together. Chamberlin is "basic" when applied to magnesium salts. (basic) "is defined as:" basic magnesium salt and other Basic alkaline earth metal salts are ... excess magnesium or other alkaline earth It is called a basic salt because it contains a metal cation. Generally, basic or hyperbasic The salt has a metal ratio of about 2 to about 30 or 40. "Chambourine burns alcohol High when used in a fuel engine or an alcohol / gasoline mixed fuel engine His lubricant containing a concentration of basic (ie metal ratio ≧ 2) magnesium was Alcohol. Claiming to minimize the problems of corrosive wear and pre-ignition associated with fuel-fuel engines I have. Chamberlin also distributed his lubricant to meet the API SG classification. Insist that they can. Chamberlin's patent is a soot-related increase in viscosity And peculiar problems related to forming piston deposits in diesel engines Not something.   Using Group II Metal Hydrocarbyl Sulfonates to Achieve High TNB Another method patent, which is otherwise harmful Recognized patent is Rollin's European Patent No. 277,729 . The composition of lorin has a first (1 °) to second (2 °) ratio of about 1: 1 to about 5 :. Zinc dithiophosphate, having both first and second attributes to be 1, succinimine The total TNB in the finished oil is at least 8. He is succinimide Is required to pass the friction test and the upper limit of the amount of succinimide present is It says that it does not matter for performance, but it is decided only by cost. . Lorin has reported quite a few engine tests, but the Mac T-7 results show Not. He also found that dihydrocarbyldithio was made from a secondary alcohol. The results of the test when the metal salt of orthophosphoric acid exceeds the amount produced from the primary alcohol Not shown.   Di-diene made from certain secondary alcohols and used with certain dispersants All other patents relating to the use of zinc thiophosphate are U.S. Pat. No. 4,904,40 to Ripple. No. 1, No. 4,957,649, and No. 4,981,602.   Other than the patents mentioned above, there are other documents related to the need to meet performance requirements in this technology. There are many in the field. The European patent publication of Carroll et al. A cost-effective crankcase lubricant is the first dihydrocarbyl dithiophosphate The amount of lead (ZDDP) is balanced with respect to the second ZDDP (first ZDDP vs. second ZDDP). 0.4: 1 to 9: 1) based on the weight of It is a cleaning agent, and the amount of the overbased calcium detergent is equivalent to that of the overbased magnesium detergent. Balanced (0.1: 1 to 6: 1 by weight of metal) It is taught to be obtained by using.   Despite all the research done so far, In the Zell test (including Mac T-8 and Caterpillar 1N) It shows extremely good performance without sacrificing performance and is resistant to oxidation, rust, and wear. Moisture intended for use in gasoline fueled engines such as excellent resistance The demand for lubricants that provide the highest API classification requirements for lubricants depends on It exists as it is.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI C10M 159: 20 159: 22 159: 24) C10N 10:04 40:04 60:14 (81) Designated country EP ( AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), AU, CA, JP, SG (72) Inventor Outen, Edward ・Francis U.S.A. New Jersey 08816, East Brunswick, Corona Road 17 (72) Inventor Ritchie, Andrew James D'Azile, New Jersey 07928, Chatham, Canterbury Road 83 (72) Inventor Wadope, Malcolm, New Jersey, USA Witchview Drive 7 Westfield, West 07090

Claims (1)

[Claims] 1. Contains 0.35 to 2% by weight of sulfated ash and contains a major amount of oil of lubricating viscosity A crankcase lubricant, in which the oil contains   A) Ashless nitrogen-containing dispersant, ashless nitrogen-containing dispersant viscosity modifier, oil-soluble aliphatic, o A group consisting of xyalkyl or arylalkylamines, and mixtures thereof A nitrogen-containing TBN source selected from   B) Metal salts of oil-soluble acids with TBN greater than 100,   C) An amount of magnesium salt that gives at least 500 ppm (mass) of magnesium. ,     as well as   D) at least one metal salt of dihydrocarbyl dithiophosphate, Is added and the nitrogen-containing TBN source provides the lubricant with at least about 1.5 TBN The metal salt of the soluble acid provides at least about 40% of the total TBN of the composition, and At least 50 mol% of the hydrocarbyl groups on the metal rubyldithiophosphate are secondary. A lubricant. 2. The metal salt of an oil-soluble acid having a TBN of more than 100 is a metal salt of an oil-soluble sulfonic acid. The lubricant of claim 1, wherein 3. It also gives 500 ppm (mass) magnesium, which requires a metal salt of oil-soluble sulfonic acid. The lubricant according to claim 2, which is a magnesium salt. 4. Effective formation of aromatic amines having at least two aromatic groups directly bonded to nitrogen Lubricant according to claim 1, characterized in that it contains only 0.2% by weight or less. 5. Further comprising a boron-containing additive in an amount to provide at least 100 ppm (mass) of boron. The lubricant according to claim 1. 6. The lubricant of claim 5, wherein the ratio of boron to nitrogen is greater than 0.1. 7. The lubricant of claim 1 comprising at least 1000 ppm (mass) phosphorus. 8. A) Ashless nitrogen-containing dispersants, oil-soluble aliphatic, oxyalkyl, or aryl A nitrogen-containing TBN source selected from the group consisting of rukylamines, and mixtures thereof,   B) Metal salts of oil-soluble acids with TBN greater than 100,   C) An amount of magnesium salt that gives at least 3100 ppm (mass) of magnesium. ,     as well as   D) at least one metal salt of dihydrocarbyl dithiophosphate,   Wherein the nitrogen-containing TBN source provides the concentrate with at least about 10 TBN. , Metal salts of oil-soluble acids give at least about 40% of the total TBN of the concentrate, and dihydric acid At least 50 mol% of the hydrocarbyl groups on the metal salt of rocarbyl dithiophosphate are secondary. It's a concentrate. 9. Contains 0.35 to 2% by weight of sulfated ash and contains a major amount of oil of lubricating viscosity A crankcase lubricant, in which the oil contains   A) Ashless nitrogen-containing dispersant, ashless nitrogen-containing dispersant viscosity modifier, oil-soluble aliphatic, o A group consisting of xyalkyl or arylalkylamines, and mixtures thereof A nitrogen-containing TBN source selected from   B) Metal salts of oil-soluble acids with TBN greater than 100,   C) An amount of magnesium salt that gives at least 500 ppm (mass) of magnesium. ,     as well as   D) at least one metal salt of dihydrocarbyl dithiophosphate,   E) at least 0.0008 mol% oil-soluble hindered phenolic antioxidant, Is added and the nitrogen-containing TBN source provides the lubricant with at least about 1.5 TBN The metal salt of the soluble acid provides at least about 40% of the total TBN of the composition, the dihydrocarbyl At least 50 mol% of the hydrocarbyl groups on the metal dithiophosphate are secondary and The lubricant is an aromatic amine having at least two aromatic groups directly bonded to nitrogen. Contains no lubricant. Ten. At least 75 mol% of hydrocarbyl groups on dihydrocarbyl dithiophosphate Is a second crankcase lubricant according to claim 1, 3, 5, 7, or 9. 11. Contains 0.35 to 2% by weight of sulfated ash and contains a major amount of oil of lubricating viscosity A crankcase lubricant, in which the oil contains   A) Ashless nitrogen-containing dispersant, ashless nitrogen-containing dispersant viscosity modifier, oil-soluble aliphatic, o A group consisting of xyalkyl or arylalkylamines, and mixtures thereof A nitrogen-containing TBN source selected from   B) Metal salts of oil-soluble acids with TBN greater than 100,   C) An amount of magnesium salt that gives at least 500 ppm (mass) of magnesium. ,     as well as   D) at least one metal salt of dihydrocarbyl dithiophosphate,   E) at least 0.0008 mol% oil-soluble hindered phenolic antioxidant,   F) a boron-containing additive in an amount that provides at least 100 ppm (mass) of boron, Is added and the nitrogen-containing TBN source provides the lubricant with at least about 1.5 TBN The metal salt of the soluble acid provides at least about 40% of the total TBN of the composition, the dihydrocarbyl At least 75 mol% of the hydrocarbyl groups on the metal dithiophosphate are secondary and Lubricants include aromatic amines with at least two aromatic groups attached directly to the nitrogen , Contains at least 1000 ppm (mass) of phosphorus, and the ratio of boron to nitrogen is Greater than 0.1, lubricant.