EP0768367A1 - Schmiermittelzusammensetzung - Google Patents

Schmiermittelzusammensetzung Download PDF

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Publication number
EP0768367A1
EP0768367A1 EP96307408A EP96307408A EP0768367A1 EP 0768367 A1 EP0768367 A1 EP 0768367A1 EP 96307408 A EP96307408 A EP 96307408A EP 96307408 A EP96307408 A EP 96307408A EP 0768367 A1 EP0768367 A1 EP 0768367A1
Authority
EP
European Patent Office
Prior art keywords
lubricating
oil
base
weight
lubricating composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96307408A
Other languages
English (en)
French (fr)
Other versions
EP0768367B1 (de
Inventor
Noriyoshi Asahi Denka Kogyo K.K. Tanaka
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.)
Adeka Corp
Original Assignee
Adeka Corp
Asahi Denka Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP26434495A external-priority patent/JPH09104886A/ja
Priority claimed from JP28522895A external-priority patent/JPH09125082A/ja
Application filed by Adeka Corp, Asahi Denka Kogyo KK filed Critical Adeka Corp
Publication of EP0768367A1 publication Critical patent/EP0768367A1/de
Application granted granted Critical
Publication of EP0768367B1 publication Critical patent/EP0768367B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • 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
    • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
    • C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • 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
    • C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
    • C10M117/08—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
    • 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
    • C10M129/26—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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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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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
    • C10M137/10—Thio derivatives
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
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    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/082—Inorganic acids or salts thereof containing nitrogen
    • C10M2201/083—Inorganic acids or salts thereof containing nitrogen nitrites
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    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
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    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
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    • C10N2040/50—Medical uses

Definitions

  • This invention relates generally to lubricating compositions and has particular reference to a lubricant composition containing a base lubricating oil and one or more molybdenum compounds and having a sodium content of not greater than 200 ppm, and also to a grease composition containing a base lubricating grease and one or more molybdenum compounds and having a sodium content of not greater than 200 ppm.
  • the grease composition is excellent in its frictional and wearing characteristics and hence is suitably applicable to universal joints inclusive of constant velocity joints (CVJ) for automotive use, constant velocity gears and variable speed gears.
  • An engine oil generally contains, to maintain desired performance, various additives such as friction regulating additives, antioxidants, cleaning agents, dispersants, extreme pressure agents, viscosity index improvers, pour point depressants, antiwear agents and the like.
  • various additives such as friction regulating additives, antioxidants, cleaning agents, dispersants, extreme pressure agents, viscosity index improvers, pour point depressants, antiwear agents and the like.
  • 5-508188 discloses a lubricating composition in which an overbasified alkali metal salt such as of a sodium, potassium, lithium or like metal of an acidic organic compound, a dispersant, dihydrocarbyl dithiophosphate and an antioxidant are incorporated to reduce deterioration and prevent wear of the engine, and to present sludge formation.
  • an overbasified alkali metal salt such as of a sodium, potassium, lithium or like metal of an acidic organic compound
  • a dispersant, dihydrocarbyl dithiophosphate and an antioxidant are incorporated to reduce deterioration and prevent wear of the engine, and to present sludge formation.
  • organomolybdenum compounds are now being seen as essential additives.
  • Japanese Patent Laid-Open No. 5-279686 suggests that the friction characteristics of an engine oil can be improved, without wear resistance and other important qualities impaired, by formulation of an organomolybdenum compound, a fatty ester, a metallic cleaning agent (calcium sulfonate, magnesium sulfonate, calcium phenate and magnesium phenate), an ashless cleaning dispersant (benzylamine, its boron derivative, an imide of alkenyl succinate and its boron derivative) and an antiwear agent [zinc dithiophosphate (ZDTP) and zinc dithiocarbamate (ZDTC)].
  • an organomolybdenum compound a fatty ester
  • a metallic cleaning agent calcium sulfonate, magnesium sulfonate, calcium phenate and magnesium phenate
  • an ashless cleaning dispersant benzylamine, its boron derivative, an imide of alkenyl succinate and its boron derivative
  • an antiwear agent zinc di
  • CVJ Constant velocity joints
  • FF and 4WD vehicles or FR vihicles with indepedent suspension are being widely used for the rapidly growing numbers of FF and 4WD vehicles or FR vihicles with indepedent suspension.
  • CVJ's are used to transmit engine-power to the wheels, smooth power transmission is also required even in when the steering wheel has been turned left or right.
  • CVJ's are generally a plunger type joint that is axially slidable on the engine side and a fixed type joint that is fixed axially on the wheel side.
  • the plunger joint involves sliding resistance arising in the axial direction from its rolling and sliding movements as it reciprocates, thus leading to undesirable noise and vibration in an automatic transmission car, namely vibration during idling, rolling during startup and acceleration of the car, and beat frequency and entrapped noises from the car at certain speeds.
  • Vibration damping is now a significant problem in keeping with the demand for more comfortable quiter, automotive vehicles. Consequently, focus has been centered not only on improving the joints themselves
  • Molybdenum disulfide a sulfur-phosphorus type additive, a lead type additive or the like has heretofore been employed as an additive to be incorporated in a grease composition for use with constant velocity joints.
  • organomolybdenum compounds have been put to use in the production of a grease exhibiting damped vibration that is a key quality in the art, i.e., a grease with low friction performance.
  • Japanese Patent Laid-Open No. 6-184583 discloses a grease for use with constant velocity joints and also a grease composition for such joints wherein a urea grease is formulated with molybdenum dithiophosphate, molybdenum dithiocarbamate and ZDTC.
  • Engine oils are usually composed of a wide variety of additives as already discussed. In such oils, the additives tend to interact in some cases with each other and thus fail to impart their respective inherent properties.
  • greases contain additives including oiliness improvers, antiwear agents, extreme pressure agents, solid lubricants, pour point depressants, viscosity index improvers, tackifiers, structural stabilizers and the like as well as special additives including cleaning dispersants, defoamesr, antiseptics, dyes, antistatic agents, emulsifiers, demulsifiers and the like.
  • additives including oiliness improvers, antiwear agents, extreme pressure agents, solid lubricants, pour point depressants, viscosity index improvers, tackifiers, structural stabilizers and the like as well as special additives including cleaning dispersants, defoamesr, antiseptics, dyes, antistatic agents, emulsifiers, demulsifiers and the like.
  • organomolybdenum compound In order to meet the requirements for greases recently developed, it is import for organomolybdenum compound to exhibit its full physical performance. Accordingly, a formulation is required that eliminates the causes of bars to such performance.
  • the present invention seeks to provide a lubricating composition suitable for use as a lubricant composition or as a grease composition.
  • the present invention in a first aspect provides a lubricating composition comprising a base oil and an organomolybdenum compound, characterized in that the composition has a sodium content of not greater than 200 ppm.
  • the invention provides a lubricating composition
  • a lubricating composition comprising a base oil and one or more organomolybdenum compounds selected from the group consisting of sulfurized oxymolybdenum dithiocarbamates (MoDTC) represented by Formula (1) wherein R 1 to R 4 are each a hydrocarbyl group, and X 1 is an oxygen or sulfur atom; and sulfurized oxymolybdenum dithiophosphates (MoDTP) represented by Formula (2) wherein R 5 to R 8 are each a hydrocarbyl group, and X 2 is an oxygen or sulfur atom, characterized in that the composition has a sodium content of not greater than 200 ppm.
  • MoDTC sulfurized oxymolybdenum dithiocarbamates
  • MoDTP sulfurized oxymolybdenum dithiophosphates
  • the invention provides a lubricating composition
  • a lubricating composition comprising a base oil; one or more organomolybdenum compounds selected from the group consisting of MoDTC represented by Formula (1) wherein R 1 to R 4 and X 1 are as defined above; and MoDTP represented by Formula (2) wherein R 5 to R 8 and X 2 are as defined above; and one or more organozinc compounds selected from the group consisting of ZDTP represented by Formula (3) wherein a is 0 or 1/3, and R 9 and R 10 are each a hydrocarbyl group; and ZDTC represented by Formula (4) wherein R 11 and R 12 are each a hydrocarbyl group, characterized in that the composition has a sodium content of not greater than 200 ppm.
  • the lubricating composition according to the present invention contains said organomolybdenum compound as an essential component.
  • the sodium content in the present composition should be not greater than 200 ppm, preferably below 100 ppm based on total amount of the composition.
  • the total content of an alkali metal including sodium in the composition should be set to be not beyond 200 ppm, preferably below 100 ppm, more preferably less than 50 ppm.
  • alkali metals mentioned herein are those classed among Group I of the Periodic Table in which lithium, sodium, potassium, rubidium, cesium and francium are included.
  • an alkali metal such as sodium becomes introduced into the resultant lubricating composition in cases where such alkali metal has not been completely removed after it was employed as a catalyst or starting material in separating and purifying or synthesizing the desired base lubricating oil.
  • alkali metals or their salts are not being completely eliminated subsequent to their use as a catalyst or starting material in the syntheses of various additives as commonly practiced frequently.
  • Alkali metal compounds for use as starting materials and catalysts are exemplified by basic reagents such as alkali hydroxides, alkali sulfides, alkali hydrosulfides, alkali oxides, alkali alcoholates and the like, and reducing reagents such as alkali metals, alkali metal halides, alkali aluminum halides, alkali boron halides and the like.
  • the lubricating composition of the present invention is applied as a lubricating oil composition
  • additives such as for example an alkali metal type cleaning agent might often be added.
  • the use of such particular additive is not preferable in the practice of the present invention.
  • a base lubricating oil is incorporated with an alkali metal-containing thickener such as for example sodium soap, lithium soap, sodium terephthalamate or the like, instances wherein sodium nitrite or sodium sulfonate is added as a rust preventive, and instances wherein, though rarely, a cleaning dispersant is added.
  • an alkali metal-containing thickener such as for example sodium soap, lithium soap, sodium terephthalamate or the like
  • sodium nitrite or sodium sulfonate is added as a rust preventive
  • instances wherein, though rarely, a cleaning dispersant is added.
  • some alkali metal compounds are present in the resultant grease composition.
  • the organomolybdenum compounds that can be used in the present invention include, in addition to MoDTC and MoDTP, reaction products of molybdic acid with amines, oxymolybdenum organophosphates, (sulfurized) oxymolybdenum xanthate, reaction products of molybdenum with basic nitrogens, molybdenum-containing dispersants and the like.
  • MoDTC and MoDTP among these compounds are noticeably affected by the sodium content in the lubricating composition.
  • MoDTC is represented by the compounds of Formula (1) indicated above
  • MoDTP is represented by the compounds of Formula (2) shown above.
  • R 1 to R 4 and R 5 to R 8 are all hydrocarbyl groups that may be by nature saturated, unsaturated, chained, branched-chain or straight-chain. Such hydrocarbyl groups may be of an aliphatic, alicyclic or aromatic nature in which alkyl, alkenyl, alkylaryl, cycloalkyl, cycloalkenyl groups and the like are included.
  • Suitable alkyl groups are chosen from among methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, eicosyl, docosyl, tetracosyl, triacontyl, 2-octyl-dodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, branched monomethyl-isostearyl groups and the like.
  • Suitable alkenyl groups are chosen from among vinyl, ally, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl groups and the like.
  • Suitable alkylaryl groups are chosen from among phenyl, tolyl, xylyl, cumenyl, mesithyl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylpheny, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, alpha-naphthyl, beta-naphthyl groups and the like.
  • Suitable cycloalkyl and cycloalkenyl groups are chosen from among cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methyl-cyclopentenyl, methylcyclohexenyl, methylcycloheptenyl groups and the like.
  • the substituent groups, R 1 to R 8 may be the same or different; that is, R 1 to R 4 may be identical to, or different from R 5 to R 8 .
  • the base oil is a base oil for lubricating oil, i.e., where the lubricating composition is a lubricating oil composition
  • an alkyl group of 8 to 13 carbon atoms is preferred as R 1 to R 4 that are in MoDTC and an alkyl group of 6 to 13 carbon atoms as R 5 to R 8 that are in MoDTP.
  • R 1 to R 4 are different from each other, is preferable when the resultant lubricating oil composition is to have long drain or long service life.
  • the base oil is a base grease
  • a base grease i.e., when the lubricating composition is a grease composition
  • an alkyl group with a carbon number of 1 to 15, preferably of 2 to 13, more preferably of 2 to 8 is preferred as R 1 to R 4 that are related to MoDTC
  • an alkyl group with a carbon number of 1 to 15, preferably of 2 to 15, more preferably of 2 to 8 is preferred as R 5 to R 8 that are related to MoDTP.
  • Each of the X 1 in Formula (1) and X 2 in Formula (2) is an oxygen or sulfur atom and may be identical or different. Too small a number of oxygen atoms invites insufficient lubricity, and too large a number of sulfur atoms makes the finished lubricating composition highly corrosive. Where severer lubricating conditions in particular are to be met, the atomic ratio of oxygen to sulfur is preferably from 1 : 3 to 3 : 1.
  • the organomolybdenum compounds specified above can be used singly or in combination. Though not particularly restricted, the amount of such compound added is of itself limited to gain adequate lubricity and to prevent adverse sludge.
  • the organomolybdenum compound may be used in an amount of 0.005 to 0.2 percent by weight in terms of molybdenum, preferably of 0.01 to 0.1 percent by weight, based on a selected base oil.
  • organomolybdenum compounds can also be used when the lubricating composition is a grease composition.
  • a compound if added in too small an amount is ineffective for achieving sufficient friction regulation, and the compound if added in too large an amount produces no better results with uneconomical burdens.
  • the organomolybdenum compound is added in an amount of 0.01 to 10 percent by weight, preferably of 0.05 to 5 percent by weight, based on the weight of the base grease.
  • MoDTC and MoDTP tend to contain a greater content of alkali metals, particularly of sodium metals since they are synthesized usually with the use of an alkali metal compound, especially of sodium hydrosulfide.
  • MoDTC and MoDTP for use in the lubricating composition of the present invention be derived for example by the production methods stated below.
  • MoDTC can preferably be produced by the method disclosed for instance in Japanese Patent Laid-Open No. 56-12638.
  • molybdenum trioxide or molybdate salt is reacted with an alkali sulfide or alkali hydrosulfide, followed by addition of carbon disulfide and a secondary amine, and the reaction is continued at an appropriate temperature.
  • MoDTP can preferably be produced by the methods taught for instance in Japanese Patent Laid-Open Nos. 61-87690 and 61-106587. Both methods are contrived to react an alkali sulfide or alkali hydrosulfide, followed by addition of P 2 S 5 and a secondary amine, and the reaction is continued at an appropriate temperature.
  • the lubricating composition of the present invention may be incorporated further with either one or both of ZDTP and ZDTC as organozinc compounds.
  • ZDTP is represented by the compounds of Formula (3) as previously shown, and R 9 and R 10 in that formula are each hydrocarbyl groups similar to R 1 to R 8 .
  • ZDTC is represented by the compounds of Formula (4) also indicated above, and R 11 and R 12 are each hydrocarbyl groups similar to R 1 to R 8 .
  • R 9 and R 10 are each hydrocarbyl groups and may be the same or different. Both of the substituent groups may be selected, like R 1 to R 8 , from alkyl, alkenyl, alkylaryl groups and the like, among which an alkyl group of 3 to 14 carbon atoms is particularly preferred.
  • R 9 and R 10 of one or more ZDTP compounds to be used more than 60% are preferably occupied by a primary alkyl group.
  • the remaining quantity of less than 40% may be a secondary alkyl and/or a tertiary alkyl group.
  • a is 0 or 1/3, and the resulting compound is termed a "neutral ZnDTP" when a is zero and a “basic ZnDTP” when a is 1/3.
  • ZDTP to be used in the present invention can be obtained by the method disclosed for instance in Japanese Patent Laid-Open No. 48-37251. That is, P 2 S 5 is reacted with a given alcohol to form an alkyl-substituted dithio-phosphoric acid which is then neutralized or basified with zinc oxide, whereby a zinc salt is prepared.
  • R 11 and R 12 are each hydrocarbyl groups and may be the same or different.
  • the two substituent groups are selected, like R 1 to R 8 , from alkyl, alkenyl, alkylaryl groups and the like, among which an alkyl group of 3 to 14 carbon atoms is particularly preferred.
  • One or more members of the above organozinc compounds can be used in the lubricating composition of the present invention.
  • this composition When this composition is applied as a lubricating oil composition, no particular restriction is placed on the amount of the organozinc compound to be added. Too small an amount of such compound, however, results in an insufficient level of extreme pressure performance. Conversely, too large an amount of the compound is responsible for impaired properties of extreme pressure performance and oxidation resistance.
  • ZDTP as it contains phosphorus it tends to contaminate catalysts employed inexhaust gas-treating systems.
  • the organozinc compound is therefore added in an amount of 0.005 to 2% by weight, preferably of 0.01 to 1% by weight, based on the weight of the base lubricating oil selected.
  • the organozinc compound contributes to improvements in extreme pressure performance and oxidation resistance of the lubricant composition.
  • the amount of the organozinc compound to be used is not particularly restricted. Needless to say, if too little of such compound is added a sufficient level of extreme pressure performance cannot be effectively gain and if too much is added it will be prone to poor lubricity.
  • the amount of the organozinc compound therefore, is added in an amount of 0.01 to 10% by weight, preferably of 1 to 5% by weight, based on the weight of the base lubricating grease selected. Further, the organozinc compound plays a role in improving the friction reduction perfomance of the grease composition.
  • the lubricating composition of the present invention is comprised of a base oil, one or more organomolybdenum compounds as specified above and, if desired, one or more organozinc compounds as previously stated.
  • the base oil may be a base oil for lubricating oil or a base grease.
  • the base oil for lubricating oil that can be used as the base oil may be mineral or synthetic oils.
  • mineral oil is meant such derived from cracking of crude oil and from subsequent distillation and refining. Included in the term mineral oil is paraffinic oils, naphthenic oils and oils made available from hydrogenation and solvent refining thereof.
  • synthetic oil denotes a chemically synthesized lubricating oil and includes poly-alpha-olefins, polyisobutylene (polybutenes), diesters, polyol esters, phosphate esters, silicate esters, polyalkylene glycols, polyphenylethers, silicones, fluorine compounds, alkyl benzenes and the like.
  • the lubricating composition of the present invention is used as an engine oil composition
  • it is preferred to select as the base a mineral oil such as hydrogenated oils and hydrogenation refined oils, synthetic oils such as poly-alpha-olefins, diesters, polyol esters and the like.
  • the base greases that can be used as the base oil are composed of a base lubricating oil and a thickener.
  • Suitable examples of the thickener are soap thickners such as of aluminum, barium, calcium and the like, complex soap thickners such as of complex calcium, complex aluminum and the like, urea compounds such as aromatic diureas, aliphatic diureas, alicyclic diureas, triureas, tetraureas and the like, organic non-soap thickners such as terephthalates and the like, inorganic non-soap thickeners such as bentonites, silca aerogels and the like.
  • ureas are particulary preferred, diureas more preferred and aromatic diureas most preferred.
  • the thickeners are usually used alone, but two or more members may be used in combination if desired. Though not restricted, the thickener is added usually in an amount of 3 to 40 percent by weight, preferably of 5 to 20 percent by weight, based on the weight of the base grease.
  • the base lubricating oils that can be used in the base grease may be selected from various base lubricating oils such as those of a mineral class, those of a synthetic class and blends thereof which have been commonly employed for greases.
  • the mineral oil type base lubricating oils may include those resulting from refining of crude oil by means of solvent refining, hydrogenation refining or the like, or combinations thereof.
  • the synthetic oil type base lubricating oils may include alpha-olefin polymers such as alpha-olefin oligomers of 3 to 12 carbon atoms, sebacates such as 2-ethylhexyl sebacates and dioctyl sebacates, dialkyl diesters of 4 to 12 carbon atoms such as azelates and adipates, polyol esters such as trimethylolpropane, esters resulting from reaction of pentaerythritol and monobasic acids of 3 to 12 carbon atoms, alkyl benzenes having an alkyl group of 9 to 40 carbon atoms, polyglycols such as polyglycols derived from condensation of butyl alcohol with propylene oxides, phenylethers having about 2 to 5 ether chains and about 3 to 6 phenyl groups, synthetic oils of a silicone class and synthetic oils of a fluorine class such as perfluoroalkyl polyethers.
  • the amount of the base lubricating oil to be added is usually in the range of 60 to 97 percent by weight, preferably of 80 to 95 percent by weight, based on the weight of the base grease.
  • said base grease containing the base lubricating oil and thickener in the above stated proportion have a worked consistency of 175 to 400 at 25 ⁇ C, preferably of 205 to 310.
  • lubricating composition of the present invention is used as a lubricating oil composition
  • numerous known additives may be incorporated which are chosen from friction relaxants such as higher fatty acids, higher alcohols, amines, esters and the like, extreme pressure agents such as of a sulfur, chlorine, phosphorus or organometallic type or the like, antioxidants such as phenols, amines and the like, cleaning agents such as sulfonates, phenates, carboxylates and the like of neutral or highly basic alkaline earth metals, dispersants such as imide succinates, benzyl-amines and the like, viscosity index improvers such as high-molecular poly(meth)acrylates, polyisobutylenes, polystyrenes, ethylene-propylene copolymers, styrene-isobutylene copolymers and the like, defoamers such as esters, silicones and the like, rust preventives, pour point depressants and molybdic
  • the lubricating oil composition having the formulation as stated above can be used as a lubricant for internal combustion engines such as engines for vehicles inclusive of automobiles, 2-cycle engines, aircraft engines, marine engines, locomotive engines (irrespective of whether the combustion system is gasoline, diesel, gas or turbine), as an automatic transmission fluid, as a trans axle lubricant, as a gear lubricant and as a metal working lubricant.
  • internal combustion engines such as engines for vehicles inclusive of automobiles, 2-cycle engines, aircraft engines, marine engines, locomotive engines (irrespective of whether the combustion system is gasoline, diesel, gas or turbine), as an automatic transmission fluid, as a trans axle lubricant, as a gear lubricant and as a metal working lubricant.
  • lubricating composition of the present invention is used as a grease composition
  • various known additives may be incorporated which are chosen from friction relaxants such as higher fatty acids, higher alcohols, amines, esters and the like, extreme pressure agents such as of a sulfur, halogen, phosphorus or lead type or the like, antioxidants such as phenols, amines, sulfurs, seleniums and the like, rust preventives such as long-chain carboxylic acids and their derivatives, sulfonate salts, amines, phosphate esters and their salts and the like, solid lubricants such as graphites, molybdenum disulfides, polyethylenes, polytetrafluoroethylenes (PTFE), boron nitrides and the like, pour point depressants, viscosity index improvers, tackifiers, structural stabilizers, cleaning dispersants, antiseptics, defoamers, colorants, cleaning agents such as of neutral or highly basic alkaline earth metals
  • the grease composition having the formulation as stated above according to the present invention is suited for universal joints inclusive of constant velocity joints for automotive use, constant velocity gears and variable speed gears for automotive use as well as for various other fields of application.
  • a novel lubricating oil composition which exhibits good performance of friction reduction.
  • a novel grease composition which excels in frictional and wear characteristics.
  • Base oil for lubricating oil is Base oil for lubricating oil
  • a high VI oil of a mineral class derived by subjecting a crude oil-induced mineral oil to a hydrocracking process kinematic viscosity: 4.1 cSt at 100 ⁇ C; VI: 126; sodium content: below 10 ppm.
  • a base grease obtained by mixing a low-refined mineral oil of 16.7 cSt at 100 ⁇ C with a sodium soap (a thickener), followed by uniform dispersion of the mixture for a worked consistency to reach 271 at 25 ⁇ C.
  • R 11 to R 12 2-ethylhexyl group in Formula (4); sodium content: below 10 ppm.
  • the sodium content of each of the above components was measured by an ICP process after incineration. No alkali metals other than a sodium metal were detected in the base oil for lubricating oil, base grease 1, Mo compounds 1 to 4, ZDTP, ZDTC or cleaning agents 1 to 3.
  • the resulting lubricant compositions were examined for their coefficients of friction.
  • Friction coefficient measurements were carried out with an SRV measuring apparatus and under the set of conditions indicated below.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP96307408A 1995-10-12 1996-10-11 Schmiermittelzusammensetzung Expired - Lifetime EP0768367B1 (de)

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JP26434495A JPH09104886A (ja) 1995-10-12 1995-10-12 低アルカリ金属潤滑油組成物
JP264344/95 1995-10-12
JP285228/95 1995-11-01
JP28522895A JPH09125082A (ja) 1995-11-01 1995-11-01 低アルカリ金属グリース組成物

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US20080234150A1 (en) * 2005-11-22 2008-09-25 Mitsuhiro Kakizaki Grease composition for constant velocity joint and constant velocity joint
EP2660305A4 (de) * 2010-12-29 2014-07-23 Ntn Toyo Bearing Co Ltd Schmierfettzusammensetzung, mit schmiermittel vorgeschmiertes lager, universalgelenk und linearbewegungsvorrichtung

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Publication number Priority date Publication date Assignee Title
US20080234150A1 (en) * 2005-11-22 2008-09-25 Mitsuhiro Kakizaki Grease composition for constant velocity joint and constant velocity joint
US8377858B2 (en) * 2005-11-22 2013-02-19 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint and constant velocity joint
US20130079158A1 (en) * 2005-11-22 2013-03-28 Ntn Corporation Grease composition for constant velocity joint and constant velocity joint
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EP2660305A4 (de) * 2010-12-29 2014-07-23 Ntn Toyo Bearing Co Ltd Schmierfettzusammensetzung, mit schmiermittel vorgeschmiertes lager, universalgelenk und linearbewegungsvorrichtung
US9139793B2 (en) 2010-12-29 2015-09-22 Ntn Corporation Grease composition, grease-packed bearing, universal joint and linear motion device

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EP0768367B1 (de) 2012-07-25

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