EP0609623B1 - Low phosphorous engine oil compositions and additive compositions - Google Patents
Low phosphorous engine oil compositions and additive compositions Download PDFInfo
- Publication number
- EP0609623B1 EP0609623B1 EP93310287A EP93310287A EP0609623B1 EP 0609623 B1 EP0609623 B1 EP 0609623B1 EP 93310287 A EP93310287 A EP 93310287A EP 93310287 A EP93310287 A EP 93310287A EP 0609623 B1 EP0609623 B1 EP 0609623B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- boron
- low
- oil composition
- compound
- lubricating oil
- 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
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- 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
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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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- C10M129/02—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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- C10M129/56—Acids of unknown or incompletely defined constitution
- C10M129/58—Naphthenic acids
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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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- C10M2227/00—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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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.
- 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 boron-containing ashless dispersant, 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 a dithiocarbamate compound.
- the zinc dithiophosphate is a secondary alkyl type.
- the boron-containing ashless 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.
- dithiocarbamate compounds include metal salts of dithiocarbamate compounds, such as zinc dithiocarbamate, copper dithiocarbamate, or molybdenum dithiocarbamate.
- dithiocarbamate compounds having the formula: where R 1 , R 2 , R 3 and R 4 are the same or different and each represents an alkyl group of 1 to18 carbon atoms, and (X) represents S, S-S, S-CH 2 -S, S-CH 2 -CH 2 -S, S-CH 2 -CH 2 -CH 2 -S, or S-CH 2 -CH(CH 3 )-S.
- R 1 , R 2 , R 3 and R 4 are independently selected from alkyl groups having 1 to 6 carbon atoms. More preferably, the dithiocarbamate compound is methylene bis(dibutyldithiocarbamate).
- This invention can further involve an additive concentrate having100 weight parts of a metal-containing detergent, from 10 to 700 weight parts of a boron-containing ashless dispersant, and from 1 to 200 weight parts of the antiwear agent described above.
- the present invention resides in an engine oil composition
- a metal-containing detergent comprising a metal-containing detergent, zinc dithiophosphate, a boron-containing ashless dispersant, and an antiwear agent having an aliphatic amide compound and a dithiocarbamate compound.
- metal-containing detergents zinc dithiophosphate, boron-containing ashless dispersants 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.
- boron-containing ashless dispersants 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 ashless dispersants is 0.1-5 wt.% (especially 0.2-2 wt.%).
- the particularly preferable boron-containing ashless dispersant is a succinimide derivative containing boron in an amount of 0.1-5 wt.%.
- the boron-containing ashless 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 boron-containing ashless dispersants 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 acid 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 dithiocarbamate compound that can be used in the engine oil composition of the invention is an alkyl-thiocarbamoyl compound represented by the following formula: wherein R 1 , R 2 , R 3 and R 4 are the same or different and each represents an alkyl group of 1-18 carbon atoms, and (X) represents S, S-S, S-CH 2 -S, S-CH 2 -CH 2 -S, S-CH 2 -CH 2 -CH 2 -S, or S-CH 2 -CH(CH 3 )-S.
- R 1 , R 2 , R 3 and R 4 are the same or different and each represents an alkyl group of 1-18 carbon atoms
- (X) represents S, S-S, S-CH 2 -S, S-CH 2 -CH 2 -S, S-CH 2 -CH 2 -CH 2 -S, or S-CH 2 -CH(CH 3 )-S.
- the alkyl group may be linear (straight chain) or branched chain and preferably have 1 through 10 carbon atoms, more preferably 1 through 6 carbon atoms.
- Typical alkyl groups include, for example, methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, isopentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl.
- thiocarbamate compounds of this formula are methylene bis(dibutyldithiocarbamate), bis(dimethylthiocarbamoyl)monosulfide, bis(dimethylthiocarbamoyl)disulfide, bis(dibutylthiocarbamoyl)disulfide, bis(diamyltiocarbamoyl)disulfide, and bis(dioctylthiocarbamoyl)disulfide.
- metal dithiocarbamates such as zinc dithiocarbamate, copper dithiocarbamate and molybdenum dithiocarbamate are also employable and it is particularly advantageous to use these metal dithiocarbamates. These compounds can be used singly or in combination of two or more compounds.
- 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, a boron-containing ashless dispersant, zinc dithiophosphate, and the above-mentioned aliphatic amide compound (1) and/or dithiocarbamate compound (2), 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, and 1-200 weight parts of the aliphatic amide compound and/or the dithiocarbamate compound.
- Ashless dispersant I Succinic imide
- Boron-containing ashless dispersant II Boric acid-modified succinic imide (content of boron: 0.4 wt.%)
- Metal-containing detergent Mixture of calcium sulfonate and calcium phenate
- Zinc dithiophosphate Zinc dihydrocarbyl- dithiophosphate (of secondary alkyl type having 4- 6 carbon atoms; content of phosphorus: 7.2 wt.%)
- Oxidation inhibitor Mixture of dialkyldiphenyl amine and hindered phenol
- Aliphatic amide compound Oleic amide
- Dithiocarbamate compound Molybdenum dithiocarbamate
- Viscosity index improver Ethylene-propylene copolymer derivative (dispersant type)
- Paraffinic mineral oil 100-Neutral oil having viscosity index value of 100
- the engine oil of the present invention which is prepared by incorporating a boron-containing ashless dispersant in combination with an aliphatic amide compound and with an dithiocarbamate compound 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), a boron-containing ashless dispersant, and an aliphatic amide compound and with an dithiocarbamate compound 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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Description
- 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.
- Engine oils use a mineral oil or a synthetic oil as a base oil. However, 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. Thus, 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).
- A number of such engine oil additives are known and employed in practice. Zinc dithiophosphates, for example, 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. In one embodiment, 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. In one embodiment, 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. Such lubricating compositions are useful as functional fluids in systems requiring fluid coupling, hydraulic fluid and/or lubrication of relatively moving parts, particularly as automatic transmission fluids.
- 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.
- The use of 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 R1R2N-C(S)-S-alkylene-S-C(S)-NR3R4. Example 5 of the patent describes a crankcase lubricant containing a viscosity improver, an ashless dispersant and methylene bis(dibutyldithiocarbamate). The patent further teaches that the 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.
- 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.
- The use of methylene bis(dibutyldithiocarbamate) as an oxidation inhibitor in lubricating oils, in combination with other ingredients, is also disclosed in U.S. Patent Nos. 4,125,479 and 4,880,551.
- 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. Examples 13-18 describe using Vanlube 7723 and triarylphosphate as replacements for lead naphthenate and zinc dithiophosphate.
- The use of 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-β-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.
- A problem has arisen with respect to the use of zinc dithiophosphate, because phosphorous derivatives poison catalyst components of catalytic converters. This is a major concern, because effective 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. As before mentioned these catalyst components are poisoned by the phosphorous component, or the phosphorous decomposition products of the zinc dithiophosphate; and accordingly, the use of engine oils containing phosphorous additives may substantially reduce the life and effectiveness of catalytic converters. Therefore, it would be desirable to reduce the phosphorous content in the engine oils so as to maintain the activity and extend the life of the catalytic converter.
- There is also governmental and automotive industry pressure towards reducing phosphorous content; for example, United States Military Standards MIL-L-46152E and the ILSAC Standards defined by the Japanese and United States Automobile Industry Association require engine oils to have phosphorous content below 0.12 wt. %. The phosphorous content in most high grade engine oils containing zinc dithiophosphate is approximately 0.1 wt. %, and thus meet the 0.12 wt.% requirement. Nevertheless, it would be desirable to decrease the amount of zinc dithiophosphate in lubricating oils still further, thus reducing catalyst deactivation and hence increasing the life and effectiveness of catalytic converters. However, simply decreasing the amount of zinc dithiophosphate presents problems because this necessarily lowers the antiwear properties and oxidation inhibition properties of the lubricating oil.
- Meanwhile, recent engines installed in motor cars are apt to be used to satisfy severe demands (high speed and/or high power) and the viscosity of engine oils tends to be more and more lowered to reduce viscous resistance in order to improve fuel-efficiency. For these reasons, conditions concerning lubrication of engines are becoming severer and severer, and therefore the antiwear property of engine oils is becoming more and more important. However, the known engine oils, which contain detergent-dispersant and zinc dithiophosphate as main additive components, can not satisfactorily prevent engine troubles caused by wear. Therefore, it is desired to take measures to meet this problem.
- 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 boron-containing ashless dispersant, 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 a dithiocarbamate compound.
- Preferably, the zinc dithiophosphate is a secondary alkyl type.
- Preferably, the boron-containing ashless 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.
- Included within the broad definition of dithiocarbamate compounds are metal salts of dithiocarbamate compounds, such as zinc dithiocarbamate, copper dithiocarbamate, or molybdenum dithiocarbamate.
- Also included within the broad definition of dithiocarbamate compounds are dithiocarbamate compounds having the formula: where R1, R2, R3 and R4 are the same or different and each represents an alkyl group of 1 to18 carbon atoms, and (X) represents S, S-S, S-CH2-S, S-CH2-CH2-S, S-CH2-CH2-CH2-S, or S-CH2-CH(CH3)-S. Preferably, R1, R2, R3 and R4 are independently selected from alkyl groups having 1 to 6 carbon atoms. More preferably, the dithiocarbamate compound is methylene bis(dibutyldithiocarbamate).
- This invention can further involve an additive concentrate having100 weight parts of a metal-containing detergent, from 10 to 700 weight parts of a boron-containing ashless dispersant, and from 1 to 200 weight parts of the antiwear agent described above.
- It is an object of the present invention to provide an engine oil for motor cars of which phosphorus content in lowered, but of which antiwear property is not inferior to those of the known engine oils containing zinc dithiophosphate at a conventional high content level.
- It is another object of the present invention to provide an engine oil for motor cars which shows high antiwear performance in spite of low viscosity.
- It has been found that the combination of an aliphatic amide compound with a dithiocarbamate compound gives high antiwear performance in the presence of a boron-containing ashless dispersant.
- The present invention resides in an engine oil composition comprising a metal-containing detergent, zinc dithiophosphate, a boron-containing ashless dispersant, and an antiwear agent having an aliphatic amide compound and a dithiocarbamate compound.
- A variety of metal-containing detergents, zinc dithiophosphate, boron-containing ashless dispersants 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.
- As the metal-containing detergent, 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. Generally employed 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. Also employed are other 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.
- With respect to the 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.
- Representative examples of boron-containing ashless dispersants 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 ashless dispersants is 0.1-5 wt.% (especially 0.2-2 wt.%). The particularly preferable boron-containing ashless dispersant is a succinimide derivative containing boron in an amount of 0.1-5 wt.%. The boron-containing ashless 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 boron-containing ashless dispersants can be use in combination with ashless dispersants containing no boron.
- Examples of the viscosity index improvers are 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. Typically, 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.
- Details of the aliphatic amide compound ,the dithiocarbamate compound, and the ester compound which are added into the engine oil of the invention are described below.
- A preferred aliphatic amide compound used in the engine oil composition of the invention is an amide compound of a fatty acid 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 dithiocarbamate compound that can be used in the engine oil composition of the invention is an alkyl-thiocarbamoyl compound represented by the following formula: wherein R1, R2, R3 and R4 are the same or different and each represents an alkyl group of 1-18 carbon atoms, and (X) represents S, S-S, S-CH2-S, S-CH2-CH2-S, S-CH2-CH2-CH2-S, or S-CH2-CH(CH3)-S. These are known compounds and can be prepared by known procedures, and in some cases have been employed as vulcanizing accelerators and as additives for gear oils and turbine oils and hence readily commercially available. Referring to the R1, R2, R3 and R4 groups, the alkyl group may be linear (straight chain) or branched chain and preferably have 1 through 10 carbon atoms, more preferably 1 through 6 carbon atoms. Typical alkyl groups include, for example, methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, isopentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl. Typical examples of the thiocarbamate compounds of this formula are methylene bis(dibutyldithiocarbamate), bis(dimethylthiocarbamoyl)monosulfide, bis(dimethylthiocarbamoyl)disulfide, bis(dibutylthiocarbamoyl)disulfide, bis(diamyltiocarbamoyl)disulfide, and bis(dioctylthiocarbamoyl)disulfide.
- Further, metal dithiocarbamates such as zinc dithiocarbamate, copper dithiocarbamate and molybdenum dithiocarbamate are also employable and it is particularly advantageous to use these metal dithiocarbamates. These compounds can be used singly or in combination of two or more compounds.
- The engine oil of the invention may contain various additional additives other than those described above, if desired. Examples of such additional additives include known oxidation inhibitors, extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents and pour point depressants. In addition to these additives, other antiwear agents and other multi-functional additives (e.g., organic molybdenum compounds such as molybdenum dithiophosphate) may be employed in combination.
- In the preparation of the engine oil of the invention, the additives can be added to a base oil separately. However, the engine oil is preferably prepared by beforehand producing an additive composition comprising essential components which include a metal-containing detergent, a boron-containing ashless dispersant, zinc dithiophosphate, and the above-mentioned aliphatic amide compound (1) and/or dithiocarbamate compound (2), 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, and 1-200 weight parts of the aliphatic amide compound and/or the dithiocarbamate compound.
- The invention will be further illustrated by following examples which set forth particularly advantageous method embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it.
- Various engine oils prepared from the same paraffinic mineral oil (viscosity index value: 100), viscosity index improver, pour point depressant, metal-containing detergent, zinc dithiophosphate and oxidation inhibitor; and various ashless dispersants and other additive components are set forth in Table 1. (The engine oil sample Nos. 3-4 are examples of the invention and the sample Nos. 1-2 and 5-8 are comparison examples. Every sample has a viscosity condition of SAE 5W30 and the phosphorus content of every sample is 0.08 wt.%.) With respect to wear of valve train system, the performances of these engine oil samples were evaluated by the following method.
- According to Japanese Automobile Standards Organization (JASO) M328-91, bench scale monitoring test was performed in 1.5 litter, straight 4 cylinder, OHC gasoline engine (TOYOTA type-3A) from which pistons and connecting rods had been beforehand detached. After the engine was worked by an electric motor at 1000±50 r.p.m. at 60-65 °C (oil temperature) for 200 hours, degree of scuffing (rated by scuffed area) occurring on the rocker arm pad (the face where the cam meets the rocker follower) was evaluated and presented in the form of demerit grading points 0-100 (i.e., the value of 0 means the best and the value of 100 means the worst performance).
Engine oil samples No.1 No.2 No.3 No.4 No.5 No.6 No.7 Ashless dispersant I - - - 5.0 5.0 5.0 - Boron-containing ashless dispersant II 5.0 5.0 5.0 - - - 5.0 Metal-containing detergent 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Zinc dithiophosphate 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Oxidation inhibitor 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Aliphatic amide compound 0.5 - 0.2 - 0.5 - - Dithiocarbamate compound - 0.5 0.3 - - 0.5 - Viscosity index improver 7.7 7.7 7.7 7.7 7.7 7.7 7.7 Pour point depressant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Paraffinic mineral oil 81.5 81.5 81.5 82.0 81.5 81.5 82.0 Valve train system motoring test (grading point) 1.4 2.8 0 73 26 31 11 - Further, other supplemental additives such as anti-foaming agent were added when they were required. Details of the additives set forth in Table I are as follows:
- Ashless dispersant I: Succinic imide
- Boron-containing ashless dispersant II: Boric acid-modified succinic imide (content of boron: 0.4 wt.%)
- Metal-containing detergent: Mixture of calcium sulfonate and calcium phenate
- Zinc dithiophosphate: Zinc dihydrocarbyl- dithiophosphate (of secondary alkyl type having 4- 6 carbon atoms; content of phosphorus: 7.2 wt.%)
- Oxidation inhibitor: Mixture of dialkyldiphenyl amine and hindered phenol
- Aliphatic amide compound: Oleic amide
- Dithiocarbamate compound: Molybdenum dithiocarbamate
- Viscosity index improver: Ethylene-propylene copolymer derivative (dispersant type)
- Pour point depressant: Polyalkylmethacrylate
- Paraffinic mineral oil: 100-Neutral oil having viscosity index value of 100
- As is clear from the test data set forth in Table 1, the engine oil of the present invention, which is prepared by incorporating a boron-containing ashless dispersant in combination with an aliphatic amide compound and with an dithiocarbamate compound 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), a boron-containing ashless dispersant, and an aliphatic amide compound and with an dithiocarbamate compound into lubricating base oil, shows high antiwear performance against wear of valve train system, in spite of comparatively low phosphorus content and viscosity.
Claims (23)
- A low-phosphorous lubricating oil composition for internal combustion engines comprising:(a) a major amount of a base oil of lubricating viscosity;(b) from 0.5 to 20 wt.% of metal-containing detergent;(c) from 0.1 to 3 wt.% of zinc dithiophosphate;(d) from 0.5 to 15 wt.% of boron-containing ashless dispersant; and(e) from 0.01 to 3 wt.% of an antiwear agent comprising:(i) an aliphatic amide compound; and(ii) a dithiocarbamate compound selected from the group consisting of:(a) a metal dithiocarbamate selected from the group consisting of zinc dithiocarbamate, copper dithiocarbamate, and molybdenum dithiocarbamate; and
- A low-phosphorous lubricating oil composition according to claim 1, wherein the zinc dithiophosphate is a secondary alkyl type.
- A low-phosphorous lubricating oil composition according to claim 1 or 2, wherein the boron-containing ashless dispersant comprises 0.1 to 5 wt.% boron.
- A low-phosphorous lubricating oil composition according to claim 3 wherein the boron-containing ashless dispersant comprises 0.2 to 2 wt.% boron.
- A low-phosphorous lubricating oil composition according to claim 1 or 2, wherein the boron-containing ashless dispersant is a succinimide derivative that comprises 0.1 to 5 wt.% boron.
- A low-phosphorous lubricating oil composition according to claim 5, wherein the boron-containing ashless dispersant is a succinimide derivative that comprises 0.2 to 2 wt.% boron.
- A low-phosphorous lubricating oil composition according to any one or more of the preceding claims, wherein the aliphatic amide compound is an amine compound of a fatty acid or a derivative thereof.
- A low-phosphorous lubricating oil composition according to claim 7, wherein the amine compound of a fatty acid is an amide compound of a fatty acid having from 8 to 24 carbon atoms or a derivative thereof.
- A low-phosphorous lubricating oil composition according to claim 8, wherein the amine compound of a fatty acid is an amide compound of a fatty acid having from 12 to 20 carbon atoms or a derivative thereof.
- A low-phosphorous lubricating oil composition according to claim 9, wherein the fatty acid of the amine compound is unsaturated.
- A low-phosphorous lubricating oil composition according to any one or more of claims 1 to 6, wherein the aliphatic amide compound is oleic amide or oleic amide sulfide.
- A low-phosphorous lubricating oil composition according to any one or more of the preceding claims, wherein the low-phosphorous lubricating oil composition comprises from 0.05 to 2 wt.% of the antiwear agent.
- A low-phosphorous lubricating oil composition according to any one or more of the preceding claims, wherein R1, R2, R3 and R4 are independently selected from alkyl groups having 1 to 6 carbon atoms.
- A low-phosphorous oil composition of claim 13 wherein the dithiocarbamate compound is methylene bis(dibutyldithiocarbamate).
- An additive concentrate comprising:(a) 100 weight parts of a metal-containing detergent,(b) from 10 to 700 weight parts of a boron-containing ashless dispersant, and(c) from 1 to 200 weight parts of an antiwear agent comprising:(i) an aliphatic amide compound, and(ii) a dithiocarbamate compound.
- An additive concentrate according to claim 15, wherein the boron-containing ashless dispersant comprises 0.1 to 5 wt.% boron.
- An additive concentrate according to claim 16, wherein the boron-containing ashless dispersant comprises 0.2 to 2 wt.% boron.
- An additive according to claim 15, wherein the boron-containing ashless dispersant is a succinimide derivative that comprises 0.1 to 5 wt.% boron.
- An additive concentrate according to claim 15, 16, 17 or 18, wherein the aliphatic amide compound is an amine compound of a fatty acid or derivative thereof.
- An additive concentrate according to claim 19, wherein the amine compound of a fatty acid is an amide compound of a fatty acid having from 8 to 24 carbon atoms.
- An additive concentrate according to claim 20, wherein the amine compound of a fatty acid is an amide compound of a fatty acid having from 12 to 20 carbon atoms.
- An additive concentrate according to claim 19, 20 or 21, wherein the fatty acid of the amine compound is unsaturated.
- An additive concentrate according to claim 15, 16, 17 or 18, wherein the aliphatic amide compound is oleic amide or oleic amide sulfide.
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JP35630292A JP3554757B2 (en) | 1992-12-21 | 1992-12-21 | Engine oil composition |
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US08/162,681 US5629272A (en) | 1991-08-09 | 1993-12-03 | Low phosphorous engine oil compositions and additive compositions |
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US4648985A (en) * | 1984-11-15 | 1987-03-10 | The Whitmore Manufacturing Company | Extreme pressure additives for lubricants |
US4792410A (en) * | 1986-12-22 | 1988-12-20 | The Lubrizol Corporation | Lubricant composition suitable for manual transmission fluids |
GB8704682D0 (en) * | 1987-02-27 | 1987-04-01 | Exxon Chemical Patents Inc | Low phosphorus lubricants |
US4938880A (en) * | 1987-05-26 | 1990-07-03 | Exxon Chemical Patents Inc. | Process for preparing stable oleaginous compositions |
CA1337294C (en) * | 1987-11-20 | 1995-10-10 | Dale Robert Carroll | Lubricant compositions for enhanced fuel economy |
CA1325420C (en) * | 1988-03-31 | 1993-12-21 | Armgard Kohler Everett | Lubricating oil composition |
JP2919611B2 (en) * | 1990-01-05 | 1999-07-12 | ザ ルブリゾル コーポレイション | Universal driveline fluid |
JPH0539495A (en) * | 1991-08-05 | 1993-02-19 | Tonen Corp | Lubricant oil composition |
JP3086727B2 (en) * | 1991-08-09 | 2000-09-11 | オロナイトジャパン株式会社 | Additive composition for producing low phosphorus engine oil |
-
1993
- 1993-12-20 EP EP97116487A patent/EP0814148B1/en not_active Expired - Lifetime
- 1993-12-20 EP EP93310287A patent/EP0609623B1/en not_active Expired - Lifetime
- 1993-12-20 DE DE69323717T patent/DE69323717T2/en not_active Expired - Lifetime
- 1993-12-20 SG SG1996007106A patent/SG71666A1/en unknown
- 1993-12-20 DE DE69332361T patent/DE69332361T2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0609623A1 (en) | 1994-08-10 |
DE69332361D1 (en) | 2002-11-07 |
DE69323717D1 (en) | 1999-04-08 |
EP0814148A3 (en) | 1998-01-14 |
DE69323717T2 (en) | 1999-07-01 |
EP0814148A2 (en) | 1997-12-29 |
SG71666A1 (en) | 2000-04-18 |
EP0814148B1 (en) | 2002-10-02 |
DE69332361T2 (en) | 2003-02-13 |
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