EP0814148B1 - Compositions d'huile moteur à faible teneur en phosphore, et compositions d'additifs - Google Patents

Compositions d'huile moteur à faible teneur en phosphore, et compositions d'additifs Download PDF

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Publication number
EP0814148B1
EP0814148B1 EP97116487A EP97116487A EP0814148B1 EP 0814148 B1 EP0814148 B1 EP 0814148B1 EP 97116487 A EP97116487 A EP 97116487A EP 97116487 A EP97116487 A EP 97116487A EP 0814148 B1 EP0814148 B1 EP 0814148B1
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EP
European Patent Office
Prior art keywords
amide compound
fatty acid
low
lubricating oil
oil composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97116487A
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German (de)
English (en)
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EP0814148A2 (fr
EP0814148A3 (fr
Inventor
Morikuni Nakazato
Jiro Magarifuchi
Yoshifuni Isozaki
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Chevron Oronite Japan Ltd
Original Assignee
Oronite Japan Ltd
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Filing date
Publication date
Priority claimed from JP35630292A external-priority patent/JP3554757B2/ja
Priority claimed from US08/162,681 external-priority patent/US5629272A/en
Application filed by Oronite Japan Ltd filed Critical Oronite Japan Ltd
Publication of EP0814148A2 publication Critical patent/EP0814148A2/fr
Publication of EP0814148A3 publication Critical patent/EP0814148A3/fr
Application granted granted Critical
Publication of EP0814148B1 publication Critical patent/EP0814148B1/fr
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • C10M129/58—Naphthenic acids
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M135/20—Thiols; Sulfides; Polysulfides
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    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
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    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—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
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—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
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C10M2227/062—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—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
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/063—Complexes of boron halides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—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
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—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
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to improved lubricating oils having excellent characteristics in antiwear, especially in reducing wear of valve train system. It especially relates to internal combustion engine lubricating oils, and additives and additives mixtures employable for the preparation of such lubricating oils.
  • Automobile spark ignition and diesel engines have valve train systems, including valves, cams and rocker arms which present special lubrication concerns. It is extremely important that the lubricant, i.e. the engine oil, protects these parts from wear. Further, it is important for engine oils to suppress the production of deposits in the engines. Such deposits are produced from non-combustibles and incomplete combustibles of hydrocarbon fuels (e.g., gasoline, diesel fuel oil) and by the deterioration of the engine oil employed.
  • hydrocarbon fuels e.g., gasoline, diesel fuel oil
  • Base oils use a mineral oil or a synthetic oil as a base oil.
  • simple base oils alone do not provide the necessary properties to provide the necessary wear protection, deposit control, etc. required to protect internal combustion engines.
  • base oils are formulated with various additives, for imparting auxiliary functions, such as ashless dispersants, metallic detergents (i.e., metal-containing detergents), antiwear agents, antioxidants (i.e., oxidation inhibitors), viscosity index improvers and the like to give a compounded oil (i.e., a lubricating oil composition).
  • Zinc dithiophosphates are contained in most all of the commercially available internal composition engine oils, especially those used for automobiles because of their favorable characteristics as an antiwear agent and performance as an oxidation inhibitor.
  • U.S. Patent No. 4,201,684 discloses using lubricating oils containing sulfurized fatty acid amides, sulfurized fatty acid esters, or ester-amides of alkoxylated amines, such as diethanolamine.
  • Other additives in the oils include zinc dithiophosphate, metal or sulfurized phenates, and metal hydrocarbyl sulfonates.
  • U.S. Patent No. 4,394,276 discloses using lubricating oils containing sulfur-containing alkane diols as friction reducing agents.
  • the oils also contain a metal hydrocarbyl sulfonate, a metal phenate, a zinc dithiophosphate, and a borated alkenyl succinimide or succinate or mixtures thereof.
  • U.S. Patent No. 4,394,277 discloses using lubricating oils containing borated sulfur-containing 1,2-alkane diols as friction reducing agents.
  • the oils also contain a metal hydrocarbyl sulfonate, a metal phenate, a zinc dithiophosphate, and a borated alkenyl succinimide or succinate or mixtures thereof.
  • U.S. Patent No. 4,505,829 discloses using lubricating oils containing a polycarboxylic acid-glycol ester, an oil-soluble alkenyl succinimide or borated alkenyl succinate, and either a metal hydrocarbyl sulfonate, a metal phenate, a sulfurized phenate, or a zinc dithiophosphate.
  • U.S. Patent Nos. 4,563,293 and 4,629,576 disclose using lubricating oils containing borated long-chain 1,2-alkane diols as friction reducing agents.
  • the oils also contain a metal hydrocarbyl sulfonate, a metal phenate, a zinc dithiophosphate, and a borated alkenyl succinimide or succinate or mixtures thereof.
  • U.S. Pat. No. 3,933,659 discloses lubricating oil composition which comprise a major amount of an oil of lubricating viscosity, and an effective amount of each of the following: (1) an alkenyl succinimide, (2) a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, (3) a compound selected from the group consisting of (a) fatty acid esters of dihydric and other polyhydric alcohols, and oil soluble oxyalkylated derivatives thereof, (b) fatty acid amides of low molecular weight amino acids, (c) N-fatty alkyl-N,N diethanol amines, (d) N-fatty alkyl-N,N-di(ethoxyethanol) amines, (e) N-fatty alkyl-N,N-dipoly(ethoxy) ethanol amines, and (f) mixtures thereof, and (4) a basic sulfurized alkaline earth metal alkyl phenate.
  • U.S. Pat. No. 4,032,461 discloses using a lubricating oil composition having a boron derivative of alkyenylsuccinic acid imide, zinc dithiophosphate, calcium alkylbenzene-sulfonate, and sulfurized oxymetal dithiocarbamate.
  • U.S. Pat. No. 4,960,528 discloses using in an engine crankcase a formulated motor oil containing a small amount of the combination of (i) an overbased alkaline earth metal sulfonate, (ii) a zinc dihydrocarbyl dithiophosphate, (iii) a sulfurized carboxylic acid ester, and (iv) a sulfurized fatty acid amide, ester or ester-amide of an oxyalkylated amine or mixtures thereof.
  • dithiocarbamates in lubricating oils is well known in the art.
  • U.S. Patent No. 3,876,550 discloses lubricating compositions containing an alkylene bis(dithiocarbamate), as an antioxidant, and a substituted succinic acid as a rust inhibitor.
  • the alkylene dithiocarbamate is represented in the patent by the formula R 1 R 2 N-C(S)-S-alkylene-S-C(S)-NR 3 R 4 .
  • Example 5 of the patent describes a crankcase lubricant containing a viscosity improver, an ashless dispersant and methylene bis(dibutyldithiocarbamate).
  • composition may also contain various other additives, for example, detergents, dispersants, viscosity improvers, extreme pressure agents, antiwear additives, etc., as well as other oxidation inhibitors and corrosion inhibitors and cites an extensive list of extreme pressure agents, corrosion inhibitors and antioxidants, including zinc salts of phosphorodithoic acid.
  • additives for example, detergents, dispersants, viscosity improvers, extreme pressure agents, antiwear additives, etc.
  • oxidation inhibitors and corrosion inhibitors include zinc salts of phosphorodithoic acid.
  • U.S. Patent No. 4,529,526 discloses the use of a sulfurized oxymetal dithiocarbamate with a boron derivative of alkyenylsuccinic acid imide, zinc dithiophosphate, and calcium alkylbenzene-sulfonate.
  • U.S. Patent No. 4,879,054 is directed to cold temperature greases and teaches using dithiocarbamates such as Vanlube 7723, i.e., 4,4'-methylene bis(dithiocarbamate), in such greases to provide extreme pressure antiwear properties.
  • dithiocarbamates such as Vanlube 7723, i.e., 4,4'-methylene bis(dithiocarbamate)
  • Examples 13-18 describe using Vanlube 7723 and triarylphosphate as replacements for lead naphthenate and zinc dithiophosphate.
  • dithiocarbamates as extreme pressure antiwear additives is also taught by U.S. Patent No. 4,859,352, and U.S. Patent No. 4,648,985 teaches that the combination of dithiocarbamates with zinc dithiophosphate and copper salts of carboxylic acid provide lubricants with extreme pressure properties.
  • U.S. Patent No. 4,383,931 discloses using lubricating oils containing an oil-soluble molybdenyl bis- ⁇ -diketonate in combination with zinc dithiophosphate.
  • Methylene bis(dihydrocarbyldithiocarbamates) are used as ashless antioxidants and extreme pressure agents.
  • U.S. Patent No. 4,501,678 discloses using lubricating oils containing an alkyl thiocarbamoyl compound and either a molybdenum thiocarbamoyl compound or a molybdenum organophosphorodithioate.
  • U.S. Patent No. 4,609,480 discloses using lubricating oils containing an alkyl thiocarbamoyl compound and a 1,3,4-thiadiazole compound.
  • the oils can also contain, among other things, sulfurized oxymolydenum organophosphorodithioates.
  • WO-88/04684 discloses a lubricant mixture suitable for a manual transmission fluid comprising:
  • catalytic converters are needed to reduce pollution and to meet governmental regulation designed to reduce toxic gases, such as hydrocarbons, carbon monoxide, and nitrogen oxides, in internal combustion engine exhaust emission.
  • Such catalytic converters generally use a combination of catalytic metals, such as platinum or variations, and metal oxides and are installed in the exhaust streams, e.g., the exhaust pipes of automobiles, to convert the toxic gases to nontoxic gases.
  • the present invention provides a low-phosphorous lubricating oil composition for internal combustion engines that shows high antiwear performance in spite of low viscosity.
  • That composition has a major amount of a base oil of lubricating viscosity, from 0.5 to 20 wt.% of metal-containing detergent, from 0.1 to 3 wt.% of zinc dithiophosphate, from 0.5 to 15 wt.% of an ashless dispersant that has been borated, and from 0.01 to 3 wt.% of an antiwear agent, preferably from 0.05 to 2 wt.% antiwear agent.
  • the antiwear agent has an aliphatic amide compound and an ester derived from a fatty acid and boric acid.
  • the zinc dithiophosphate is a secondary alkyl type.
  • the dispersant comprises from 0.1 to 5 wt.% boron, more preferably from 0.2 to 2 wt.% boron.
  • the preferred dispersant is a succinimide derivative.
  • the ester is derived from glycerol, boric acid and a fatty acid having 8-24 carbon atoms. That ester can have the following formulas: wherein X, Y and Z are the same or different and each represents a group selected from the group consisting of a hydroxyl group and an alkylcarboxyl group.
  • This invention can further involve an additive concentrate having 100 weight parts of a metal-containing detergent, from 10 to 700 weight parts of an ashless dispersant that has been borated, from 1 to 200 weight parts of the antiwear agent described above, and zinc dithiophosphate.
  • the present invention resides in an engine oil composition
  • a metal-containing detergent comprising a metal-containing detergent, zinc dithiophosphate, an ashless dispersant that has been borated, and an antiwear agent having an aliphatic amide compound and an ester derived from a fatty acid and boric acid.
  • a variety of metal-containing detergents, zinc dithiophosphate, ashless dispersants that have been borated and base oils are known. These known materials or their analogous compounds can be employed for the preparation of the engine oil of the invention. Further, viscosity index improvers are usually added to the engine oils in order to adjust viscosity. Representative examples of these materials are described below.
  • a metal phenate or a metal sulfonate is generally employed.
  • the metal phenate is an alkaline earth metal salt of sulfide of alkylphenol having an alkyl group of approx. 8-30 carbon atoms.
  • alkaline earth metals are calcium, magnesium and barium.
  • the metal sulfonate is an alkaline earth metal salt of a sulfonated aromatic compound or a sulfonated mineral oil having a molecular weight of approx. 400-600.
  • Generally employed alkaline earth metals are also calcium, magnesium and barium.
  • the metal phenate and metal sulfonate can be used singly or in combination.
  • metal-containing detergents such as salicylate, phosphonate and naphthenate of alkaline earth metals. These detergents can be employed single or in combination. The aforementioned phenate and sulfonate can be employed in combination with these other metal-containing detergents.
  • the metal-containing detergents may be of a neutral type or of an over-based type having an alkalinity value of 150-300 or more.
  • the metal-containing detergent is generally incorporated into an engine oil in an amount of 0.5-20 wt.% per total amount of the engine oil.
  • zinc dithiophosphate preferably used as an antiwear agent or an oxidation inhibitor is zinc dihydrocarbyldithiohosphate having an alkyl group of 3-18 carbon atoms or an alkylaryl group including an alkyl group of 3-18 carbon atoms.
  • This agent is generally incorporated into an engine oil in an amount of 0.1-3 wt.% per total amount of the engine oil.
  • ashless dispersants that have been borated are boron-containing compounds prepared by boration of succinimide, succinic ester, benzylamine and their derivatives each of which has an alkyl or alkenyl group of a molecular weight of approx. 700-3,000.
  • a preferred amount of boron contained in these dispersants is 0.1-5 wt.% (especially 0.2-2 wt.%).
  • the particularly preferable dispersant is a succinimide derivative containing boron in an amount of 0.1-5 wt.%.
  • the dispersant is generally incorporated into an engine oil in an amount of 0.5-15 wt.% per total amount of the engine oil. Needless to say, the ashless dispersants that have been borated can be use in combination with ashless dispersants containing no boron.
  • viscosity index improvers examples include poly- (alkyl methacrylate), ethylene-propylene copolymer, styrene- butadiene copolymer, and polyisoprene. Viscosity index improvers of dispersant type (having increased dispersancy) or multifunction type are also employed. These viscosity index improvers can be used singly or in combination.
  • the amount of viscosity index improver to be incorporated into an engine oil varies with desired viscosity of the compounded engine oil, and generally in the range of 0.5-20 wt.% per total amount of the engine oil.
  • the base oil may be a mineral oil or synthetic oil or a blend of mineral oils and/or synthetic oils blended to give a base oil of the desired internal combustion engine oil viscosity.
  • individually the oils used as its base oil will have a viscosity range of about from 10 to 120 cST at 40°C and will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil.
  • a preferred aliphatic amide compound used in the engine oil composition of the invention is an amide compound of a fatty add preferably having 8-24 (especially 12-20) carbon atoms or its derivative.
  • Such fatty acid may be saturated or unsaturated, but an unsaturated fatty acid is preferable.
  • Other functional groups can be Included in the acid.
  • Particularly preferable examples of the amide compound are oleic amide and oleic amide sulfide.
  • the ester that can be used in the engine oil composition of the invention is an ester derived from a fatty acid and boric acid.
  • a preferred example of such ester is an ester which is derived from glycerol, boric acid and a fatty acid having 8-24 carbon atoms and which is represented by one of the following formulae (I), (II) and (III):
  • X, Y and Z are the same or different and each represents hydroxyl group (-OH) or an alkylcarboxyl group (-OCOR: R represents an alkyl group of 7-23 carbon atoms of straight chain type or branched chain type and it may be saturated or unsaturated.)
  • the engine oil of the invention may contain various additional additives other than those described above, if desired.
  • additional additives include known oxidation inhibitors, extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents and pour point depressants.
  • other antiwear agents and other multi-functional additives e.g., organic molybdenum compounds such as molybdenum dithiophosphate may be employed in combination.
  • the additives can be added to a base oil separately.
  • the engine oil is preferably prepared by beforehand producing an additive composition comprising essential components which include a metal-containing detergent, an ashless dispersant that has been borated, zinc dithiophosphate, and the above-mentioned aliphatic amide compound, and optional components (generally dissolved or dispersed in a base oil at a high concentration); and then incorporating thus produced additive composition, a viscosity index improver and other optional components into a large amount of base oil.
  • the additive composition is preferably prepared by mixing 100 weight parts of a metal-containing detergent, 10-700 weight parts of an ashless dispersant that has been borated, and 1-200 weight parts of the aliphatic amide compound.
  • the engine oil of the present invention which is prepared by incorporating an ashless dispersant that has been borated in combination with an aliphatic amide compound and with an ester derived from a fatty acid and boric acid, shows high antiwear performance against wear of valve train system.
  • the engine oil of the present invention which is prepared by incorporating a metal-containing detergent, zinc dithiophosphate (zinc dithiophosphate), an ashless dispersant that has been borated, and an aliphatic amide compound and with an ester derived from a fatty acid and boric acid into lubricating base oil, shows high antiwear performance against wear of valve train system, in spite of comparatively low phosphorus content and viscosity.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (22)

  1. Composition d'huile lubrifiante à basse teneur en phosphore pour des moteurs à combustion interne, comprenant :
    (a) une quantité dominante d'une huile de base de viscosité propre à la lubrification ;
    (b) 0,5 à 20 % en poids d'un détergent contenant un métal ;
    (c) 0,1 à 3 % en poids de dithiophosphate de zinc ;
    (d) 0,5 à 15 % en poids d'un dispersant sans cendres qui a été boraté ; et
    (e) 0,01 à 3 % en poids d'un agent anti-usure comprenant :
    (i) un amide aliphatique ; et
    (ii) un ester dérivé d'un acide gras et de l'acide borique.
  2. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 1, dans laquelle le dithiophosphate de zinc est du type alkylique secondaire.
  3. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 1 ou 2, dans laquelle le dispersant comprend 0,1 à 5 % en poids de bore.
  4. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 3, dans laquelle le dispersant comprend 0,2 à 2 % en poids de bore.
  5. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 1 ou 2, dans laquelle le dispersant est un dérivé de succinimide qui comprend 0,1 à 5 % en poids de bore.
  6. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 5, dans laquelle le dispersant est un dérivé de succinimide qui comprend 0,2 à 2 % en poids de bore.
  7. Composition d'huile lubrifiante à basse teneur en phosphore suivant l'une quelconque des revendications précédentes, dans laquelle l'amide aliphatique est un amide d'un acide gras.
  8. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 7, dans laquelle l'amide d'un acide gras est un amide d'un acide gras ayant 8 à 24 atomes de carbone.
  9. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 8, dans laquelle l'amide d'un acide gras est un amide d'un acide gras ayant 12 à 20 atomes de carbone.
  10. Composition d'huile lubrifiante à basse teneur en phosphore suivant la revendication 9, dans laquelle l'acide gras de l'amide est insaturé.
  11. Composition d'huile lubrifiante à basse teneur en phosphore suivant une ou plusieurs quelconques des revendications 1 à 6, dans laquelle l'amide aliphatique est l'amide oléique ou le sulfure d'amide oléique.
  12. Composition d'huile lubrifiante à basse teneur en phosphore suivant une ou plusieurs quelconques des revendications précédentes, ladite composition d'huile lubrifiante à basse teneur en phosphore comprenant 0,05 à 2 % en poids de l'agent anti-usure.
  13. Composition d'huile lubrifiante à basse teneur en phosphore suivant une ou plusieurs quelconques des revendications précédentes, dans laquelle l'ester est un ester dérivé du glycérol, de l'acide borique et d'un acide gras ayant 8 à 24 atomes de carbone, ledit ester étant choisi dans le groupe consistant en :
    (1) un ester répondant à la formule :
    Figure 00260001
    (2) un ester répondant à la formule :
    Figure 00270001
    (3) un ester répondant à la formule :
    Figure 00270002
    formules dans lesquelles X, Y et Z sont identiques ou différents et représentent chacun un groupe choisi dans le groupe consistant en un groupe hydroxyle et un groupe alkylcarboxyle.
  14. Concentré d'additifs comprenant :
    (a) 100 parties en poids d'un détergent contenant un métal,
    (b) 10 à 700 parties en poids d'un dispersant sans cendres qui a été boraté, et
    (c) 1 à 200 parties en poids d'un agent anti-usure comprenant :
    (i) un amide aliphatique,
    (ii) un ester dérivé d'un acide gras et de l'acide borique, et
    (d) du dithiophosphate de zinc.
  15. Concentré d'additifs suivant la revendication 14, dans lequel le dispersant comprend 0,1 à 5 % en poids de bore.
  16. Concentré d'additifs suivant la revendication 15, dans lequel le dispersant comprend 0,2 à 2 % en poids de bore.
  17. Additif suivant la revendication 14, dans lequel le dispersant est un dérivé de succinimide qui comprend 0,1 à 5 % en poids de bore.
  18. Concentré d'additifs suivant la revendication 14, 15, 16 ou 17, dans lequel l'amide aliphatique est un amide d'un acide gras.
  19. Concentré d'additifs suivant la revendication 18, dans lequel l'amide d'un acide gras est un amide d'un acide gras ayant 8 à 24 atomes de carbone.
  20. Concentré d'additifs suivant la revendication 19, dans lequel l'amide d'un acide gras est un amide d'un acide gras ayant 12 à 20 atomes de carbone.
  21. Concentré d'additifs suivant la revendication 18, 19 ou 20, dans lequel l'acide gras de l'amide est insaturé.
  22. Concentré d'additifs suivant la revendication 14, 15, 16 ou 17, dans lequel l'amide aliphatique est l'amide oléique ou le sulfure d'amide oléique.
EP97116487A 1992-12-21 1993-12-20 Compositions d'huile moteur à faible teneur en phosphore, et compositions d'additifs Expired - Lifetime EP0814148B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP35630292 1992-12-21
JP35630292A JP3554757B2 (ja) 1992-12-21 1992-12-21 エンジン油組成物
JP356302/92 1992-12-21
US162681 1993-12-03
US08/162,681 US5629272A (en) 1991-08-09 1993-12-03 Low phosphorous engine oil compositions and additive compositions
EP93310287A EP0609623B1 (fr) 1992-12-21 1993-12-20 Compositions d'huile et d'additifs à faible teneur en phosphore

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP93310287.3 Division 1993-12-20
EP93310287A Division EP0609623B1 (fr) 1992-12-21 1993-12-20 Compositions d'huile et d'additifs à faible teneur en phosphore

Publications (3)

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EP0814148A2 EP0814148A2 (fr) 1997-12-29
EP0814148A3 EP0814148A3 (fr) 1998-01-14
EP0814148B1 true EP0814148B1 (fr) 2002-10-02

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EP97116487A Expired - Lifetime EP0814148B1 (fr) 1992-12-21 1993-12-20 Compositions d'huile moteur à faible teneur en phosphore, et compositions d'additifs

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Also Published As

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DE69332361T2 (de) 2003-02-13
DE69323717T2 (de) 1999-07-01
EP0814148A2 (fr) 1997-12-29
DE69332361D1 (de) 2002-11-07
EP0609623A1 (fr) 1994-08-10
EP0609623B1 (fr) 1999-03-03
DE69323717D1 (de) 1999-04-08
EP0814148A3 (fr) 1998-01-14
SG71666A1 (en) 2000-04-18

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