EP0609623B1 - Wenig Phosphor enthaltende Motorölzusammensetzungen und Zusatzzusammensetzungen - Google Patents

Wenig Phosphor enthaltende Motorölzusammensetzungen und Zusatzzusammensetzungen Download PDF

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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
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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
Application number
EP93310287A
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English (en)
French (fr)
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EP0609623A1 (de
Inventor
Morikuni Nakazato
Jiro Magarifuchi
Yoshifuni Isozaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Oronite Japan Ltd
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Oronite Japan Ltd
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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
Priority to EP97116487A priority Critical patent/EP0814148B1/de
Publication of EP0609623A1 publication Critical patent/EP0609623A1/de
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Publication of EP0609623B1 publication Critical patent/EP0609623B1/de
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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
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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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    • C10M129/02—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
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    • C10M129/58—Naphthenic acids
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    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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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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    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
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    • 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
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    • 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.
  • 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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Claims (23)

  1. Phosphorarme Schmierölzusammensetzung für Verbrennungsmotoren, umfassend
    (a) eine Hauptmenge Basisöl mit Schmierviskosität;
    (b) von 0,5 bis 20 Gew.% metallhaltiges Detergens;
    (c) von 0,1 bis 3 Gew.% Zinkdithiophosphat;
    (d) von 0,5 bis 15 Gew.% borhaltiges aschefreies Dispersionsmittel; und
    (e) von 0,01 bis 3 Gew.% Antiverschleißmittel, umfassend
    (i) eine aliphatische Amidverbindung und
    (ii) eine Dithiocarbamat-Verbindung, ausgewählt aus der Gruppe
    (a) Metall-Dithiocarbamat, ausgewählt aus der Gruppe Zinkdithiocarbamat, Kupferdithiocarbamat und Molybdändithiocarbamat, und
    (b) Dithiocarbamat-Verbindung der Formel
    Figure 00200001
    wobei ist: R1, R2, R3 und R4 gleich oder verschieden und jeweils unabhängig voneinander eine Alkylgruppe mit 1 bis 18 Kohlenstoffatomen, und (X) gleich S, S-S, S-CH2-S, S-CH2-CH2-S, S-CH2-CH2-CH2-S oder S-CH2-CH(CH3)-S.
  2. Phosphorarme Schmierölzusammensetzung nach Anspruch 1, wobei das Zinkdithiophosphat ein sekundäres Alkyl ist.
  3. Phosphorarme Schmierölzusammensetzung nach Anspruch 1 oder 2, wobei das borhaltige aschefreie Dispersionsmittel 0,1 bis 5 Gew.% Bor enthält.
  4. Phosphorarme Schmierölzusammensetzung nach Anspruch 3, wobei das borhaltige aschefreie Dispersionsmittel 0,2 bis 2 Gew.% Bor enthält.
  5. Phosphorarme Schmierölzusammensetzung nach Anspruch 1 oder 2, wobei das borhaltige aschefreie Dispersionsmittel ein Succinimidderivat ist, das 0,1 bis 5 Gew.% Bor enthält.
  6. Phosphorarme Schmierölzusammensetzung nach Anspruch 5, wobei das borhaltige aschefreie Dispersionsmittel ein Succinimidderivat ist, das 0,2 bis 2 Gew.% Bor enthält.
  7. Phosphorarme Schmierölzusammensetzung nach einem der vorstehenden Ansprüche, wobei die aliphatische Amidverbindung das Amin einer Fettsäure ist oder ein Derivat davon.
  8. Phosphorarme Schmierölzusammensetzung nach Anspruch 7, wobei die Aminverbindung einer Fettsäure das Amid einer Fettsäure mit 8 bis 24 Kohlenstoffatomen ist oder ein Derivat davon.
  9. Phosphorarme Schmierölzusammensetzung nach Anspruch 8, wobei die Aminverbindung einer Fettsäure das Amid einer Fettsäure mit 12 bis 20 Kohlenstoffatomen ist oder ein Derivat davon.
  10. Phosphorarme Schmierölzusammensetzung nach Anspruch 9, wobei die Fettsäure der Aminverbindung ungesättigt ist.
  11. Phosphorarme Schmierölzusammensetzung nach einem der Ansprüche 1 bis 6, wobei die aliphatische Amidverbindung ein Oleinamid oder Oleinamidsulfid ist.
  12. Phosphorarme Schmierölzusammensetzung nach einem der vorstehenden Ansprüche, wobei die phosphorarme Schmierölzusammensetzung 0,05 bis 2 Gew.% des Antiverschleißmittels enthält.
  13. Phosphorarme Schmierölzusammensetzung nach einem der vorstehenden Ansprüche, wobei R1, R2, R3 und R4 unabhängig voneinander ausgewählt sind aus Alkylgruppen mit 1 bis 6 Kohlenstoffatomen.
  14. Phosphorarme Ölzusammensetzung nach Anspruch 13, wobei die Dithiocarbamatverbindung Methylen-bis-dibutyldithiocarbamat ist.
  15. Additiv-Konzentrat, umfassend
    (a) 100 Gewichtsteile metallhaltiges Detergens,
    (b) von 10 bis 700 Gewichtsteile borhaltiges aschefreies Dispersionsmittel und
    (c) von 1 bis 200 Gewichtsteile Antiverschleißmittel, umfassend
    (i) eine aliphatische Amidverbindung und
    (ii) eine Dithiocarbamatverbindung.
  16. Additiv-Konzentrat nach Anspruch 15, wobei das borhaltige aschefreie Dispersionsmittel 0,1 bis 5 Gew.% Bor enthält.
  17. Additiv-Konzentrat nach Anspruch 16, wobei das borhaltige aschefreie Dispersionsmittel 0,2 bis 2 Gew.% Bor enthält.
  18. Additiv nach Anspruch 15, wobei das borhaltige aschefreie Dispersionsmittel ein Succinimidderivat ist, das 0,1 bis 5 Gew.% Bor enthält.
  19. Additiv-Konzentrat nach Anspruch 15, 16, 17 oder 18, wobei die aliphatische Amidverbindung die Aminverbindung einer Fettsäure ist oder ein Derivat davon.
  20. Additiv-Konzentrat nach Anspruch 19, wobei die Aminverbindung einer Fettsäure das Amid einer Fettsäure mit 8 bis 24 Kohlenstoffatomen ist.
  21. Additiv-Konzentrat nach Anspruch 20, wobei die Aminverbindung einer Fettsäure das Amid einer Fettsäure mit 12 bis 20 Kohlenstoffatomen ist.
  22. Additiv-Konzentrat nach Anspruch 19, 20 oder 21, wobei die Fettsäure der Aminverbindung ungesättigt ist.
  23. Additiv-Konzentrat nach Anspruch 15, 16, 17 oder 18, wobei die aliphatische Amidverbindung Oleinamid oder Oleinamidsulfid ist.
EP93310287A 1992-12-21 1993-12-20 Wenig Phosphor enthaltende Motorölzusammensetzungen und Zusatzzusammensetzungen Expired - Lifetime EP0609623B1 (de)

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JP35630292A JP3554757B2 (ja) 1992-12-21 1992-12-21 エンジン油組成物
JP356302/92 1992-12-21
US08/162,681 US5629272A (en) 1991-08-09 1993-12-03 Low phosphorous engine oil compositions and additive compositions
US162681 1993-12-03

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

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