# US 10,370,615 B2 · Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,615 B2 - Document ID: US10370615B2 - Status: Granted - Kind: B2 - Application number: 15/409,503 - Filed: 2017-01-18 - Published: 2018-07-19 - Granted: 2019-08-06 - Earliest claimed: 2017-01-18 - Assignees: Afton Chemical Corporation - Applicants: Afton Chemical Corporation - Inventors: Guillaume Carpentier; Paul Ransom; Kristin Fletcher - Web page: https://patentgrep.com/patent/US10370615B2 ## CPC - C10M 135/10: Sulfonic acids or derivatives thereof - C10M 129/50: monocarboxylic - C10M 139/00: Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 - C10M 159/20: Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products - F02P 5/02: non-automatically; dependent on position of personal controls of engine, e.g. throttle position - C10M 2203/1025: used as base material - C10M 2205/0285: used as base material - C10M 2207/028: Overbased salts thereof - C10M 2207/262: derived from hydroxy substituted aromatic acids, e.g. salicylates - C10M 2215/28: Amides; Imides - C10M 2219/046: Overbased sulfonic acid salts - C10M 2223/045: Metal containing thio derivatives - C10M 2227/00: Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions - C10N 2010/04: Groups 2 or 12 - C10N 2010/12: Groups 6 or 16 - C10N 2030/00: Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives - C10N 2030/02: Pour-point; Viscosity index - C10N 2030/04: Detergent property or dispersant property - C10N 2030/30: {Anti-misting} - C10N 2030/40: {Low content or no content compositions} - C10N 2030/52: {Base number [TBN]} - C10N 2040/25: Internal-combustion engines - C10N 2040/255: {Gasoline engines} - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - F02P: IGNITION, OTHER THAN COMPRESSION IGNITION, FOR INTERNAL-COMBUSTION ENGINES; TESTING OF IGNITION TIMING IN COMPRESSION-IGNITION ENGINES ({anti-pollution means for internal-combustion engines F02B17/00}; specially adapted for rotary-piston or oscillating-piston engines F02B53/12; {ignition of gas turbine plants F02C7/26; ignition of jet propulsion plants F02K9/95; starting of combustion engines F02N9/00}; ignition of combustion apparatus in general, glowing plugs F23Q; measuring of physical variables in general G01; controlling in general G05; data processing in general G06; electrical components in general see Section H; {ignition coils H01F38/12}; sparking plugs H01T13/00) - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract A lubricating oil composition and method of operating a boosted internal combustion engine. The lubricating oil composition includes greater than 50 wt. % of a base oil, one or more overbased calcium sulfonate detergent(s) and one or more overbased calcium phenate detergent(s). The calcium, boron, nitrogen, and amount of soap are maintained within certain ratios, and the total base number contribution from all detergents to the lubricating oil composition is less than 4.2 mg KOH/g of the lubricating oil composition, as measured by the method of ASTM D-2896. The lubricating oil composition and method may be effective to reduce low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to capable lubricating oil compositions. ## Claims ### Claim 1 A lubricating oil composition comprising: greater than 50 wt. % of a base oil of lubricating viscosity, based on a total weight of the lubricating oil composition; one or more overbased calcium sulfonate detergent(s) having a total base number of greater than 225 mg KOH/g, measured by the method of ASTM D-2896, and one or more overbased calcium phenate detergent(s) having a total base number of greater than 170 mg KOH/g, measured by the method of ASTM D-2896, wherein a ratio of the ppm of calcium in the lubricating oil composition from the one or more overbased calcium sulfonate detergent(s) to the ppm of calcium in the lubricating oil composition from the one or more overbased calcium phenate detergent(s) is greater than 1.20 to less than about 1.51, a ratio of total ppm of nitrogen in the lubricating oil composition to total wt. % of soap from the detergents in the lubricating oil composition is greater than about 2080, and a total base number contribution from all detergents is less than 4.2 mg KOH/g of the lubricating oil composition, as measured by the method of ASTM D-2896. ### Claim 2 (depends on 1) The lubricating oil composition of claim 1, wherein a ratio of total ppm of calcium in the lubricating oil composition to a total base number in mg KOH/g of the lubricating oil composition is less than about 240, as measured by the method of ASTM D-2896. ### Claim 3 (depends on 1) The lubricating oil composition of claim 1, wherein a ratio of total ppm of calcium in the lubricating oil composition to total ppm of nitrogen in the lubricating oil composition is less than 1.62. ### Claim 4 (depends on 1) The lubricating oil composition of claim 1, wherein the lubricating oil composition comprises boron in an amount of less than 300 ppm by weight. ### Claim 5 (depends on 1) The lubricating oil composition of claim 1, wherein the one or more overbased calcium sulfonate detergent(s) has a total base number of at least 250 mg KOH/g. ### Claim 6 (depends on 1) The lubricating oil composition of claim 1, wherein the lubricating oil composition is an engine oil which is effective to reduce a number of low-speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to a number of low-speed pre-ignition events in the same engine lubricated with reference lubricating oil C-1, wherein reference lubricating oil C-1 was formulated from about 80.7 wt. % of a Group III base oil, about 12.1 wt. % of passenger car motor oil additive package and about 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity index improver, wherein the passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package, and C-1 also showed the following properties and partial elemental analysis: Reference Oil C-1 10.9 Kinematic Viscosity at 100° C. (mm2/sec) 3.3 TBS, APPARENT_VISCOSITY, cPa 2400 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 770 phosphorus (ppmw) 850 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g of the lubricating oil composition) 165 Viscosity index. ### Claim 7 (depends on 6) The engine oil composition of claim 6, wherein the reduction of the number of low-speed pre-ignition events is an 85% or greater reduction and the number of low-speed pre-ignition events are a number of low-speed pre-ignition counts during 25,000 engine cycles, wherein the engine is operated at 2000 revolutions per minute with brake mean effective pressure of 1,800 kPa. ### Claim 8 (depends on 1) The lubricating oil composition of claim 1, wherein the one or more overbased calcium phenate detergent(s) is present in an amount to provide from 100 ppm to less than 910 ppm calcium to the lubricating oil composition. ### Claim 9 (depends on 1) The lubricating oil composition of claim 1, wherein the one or more overbased calcium sulfonate detergent(s) is present in an amount to provide from less than 1000 ppm calcium to the lubricating oil composition. ### Claim 10 (depends on 1) The lubricating oil composition of claim 1, wherein a total base number contribution from all detergents to the lubricating oil composition is 2.0 to less than 4.2 mg KOH/g of the lubricating oil composition, as measured by the method of ASTM D-2896. ### Claim 11 (depends on 1) The lubricating oil composition of claim 1, wherein the lubricating oil composition has a total base number less than 7.5 mg KOH/g of the lubricating oil composition, as measured by the method of ASTM D-2896. ### Claim 12 (depends on 1) The lubricating oil composition of claim 1, further comprising one or more component(s) selected from the group consisting of friction modifiers, antiwear agents, dispersants, antioxidants, and viscosity index improvers. ### Claim 13 (depends on 1) The lubricating oil composition of claim 1, wherein the greater than 50 wt. % of the base oil is selected from the group consisting of Group II, Group III, Group IV, Group V base oils, and a combination of two or more of the foregoing, and wherein the greater than 50 wt. % of the base oil is other than diluent oils that arise from provision of additive components or viscosity index improvers to the lubrication oil composition. ### Claim 14 (depends on 2) The lubricating oil composition of claim 2, wherein the ratio of the ppm of calcium in the lubricating oil composition from the one or more overbased calcium sulfonate detergent(s) to the ppm of calcium in the lubricating oil composition from the one or more overbased calcium phenate detergent(s) is greater than 1.20 to 1.45. ### Claim 15 (depends on 14) The lubricating oil composition of claim 14, wherein the total calcium provided to the lubricating oil composition by the one or more overbased calcium phenate detergent(s) is from 100 ppm to less than 910 ppm by weight, based on the total weight of the lubricating oil composition. ### Claim 16 (depends on 1) The lubricating oil composition of claim 1, which is free of added magnesium from a magnesium-containing detergent. ### Claim 17 (depends on 1) The lubricating oil composition of claim 1, further comprising one or more molybdenum-containing compound(s) in an amount sufficient to provide greater than about 80 ppm to less than 350 ppm of molybdenum to the lubricating oil composition. ### Claim 18 (depends on 1) A method for reducing a number of low-speed pre-ignition events in a boosted internal combustion engine comprising steps of: lubricating a boosted internal combustion engine with a lubricating oil composition D-2896 according to claim 1, and operating the engine lubricated with the lubricating oil composition. ### Claim 19 (depends on 18) The method of claim 18, wherein the number of low-speed pre-ignition events are based on a number of low-speed pre-ignition counts during 25,000 engine cycles, wherein the engine is operated at 2000 revolutions per minute with brake mean effective pressure of 1,800 kPa and the low-speed pre-ignition events in the boosted internal combustion engine lubricated with the lubricating oil composition are reduced relative to a number of low-speed pre-ignition events in the same engine lubricated with reference lubricating oil C-1, wherein reference lubricating oil C-1 was formulated from about 80.7 wt % of a Group III base oil, about 12.1 wt. % of passenger car motor oil additive package and about 7.2 wt. % of a 35 SSI ethylene/propylene copolymer viscosity index improver, wherein the passenger car motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 qualified DI package, and C-1 also showed the following properties and partial elemental analysis: Reference Oil C-1 10.9 Kinematic Viscosity at 100° C. (min/sec) 3.3 TBS, APPARENT_VISCOSITY, cPa 2400 calcium (ppmw) <10 magnesium (ppmw) 80 molybdenum (ppmw) 770 phosphorus (ppmw) 850 zinc (ppmw) 9.0 Total Base Number ASTM D-2896 (mg KOH/g of the lubricating oil composition) 165 Viscosity index. ### Claim 20 (depends on 18) The method of claim 18, wherein the ratio of the ppm of calcium in the lubricating oil composition from the one or more overbased calcium sulfonate detergent(s) to the ppm of calcium in the lubricating oil composition from the one or more overbased calcium phenate detergent(s) is from greater than 1.20 to 1.45. ### Claim 21 (depends on 18) The method of claim 18, wherein the lubricating step lubricates turbocharger or supercharger components and a combustion chamber or cylinder walls of a spark-ignited direct injection engine provided with a turbocharger or a supercharger or a port fuel injection internal combustion engine provided with a turbocharger or a supercharger. ### Claim 22 (depends on 21) The method of claim 21, further comprising a step of measuring the number of low-speed pre-ignition events of the internal combustion engine lubricated with the lubricating oil composition.