EP1500693A1 - Schmiermittelzusammensetzung - Google Patents

Schmiermittelzusammensetzung Download PDF

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Publication number
EP1500693A1
EP1500693A1 EP03719158A EP03719158A EP1500693A1 EP 1500693 A1 EP1500693 A1 EP 1500693A1 EP 03719158 A EP03719158 A EP 03719158A EP 03719158 A EP03719158 A EP 03719158A EP 1500693 A1 EP1500693 A1 EP 1500693A1
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Prior art keywords
group
isomers
phosphate
grease composition
general formulas
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EP03719158A
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English (en)
French (fr)
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EP1500693A4 (de
Inventor
Hirotsugu Nippon Oil Corporation Kinoshita
Souichi NIPPON OIL CORPORATION NOMURA
Takashi NIPPON OIL CORPORATION ARAI
Kiyomi NIPPON OIL CORPORATION SAKAMOTO
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Eneos Corp
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Nippon Oil Corp
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Publication of EP1500693A1 publication Critical patent/EP1500693A1/de
Publication of EP1500693A4 publication Critical patent/EP1500693A4/de
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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
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/12—Oxidised hydrocarbons, i.e. oxidised subsequent to macromolecular formation
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives

Definitions

  • the present invention relates to a grease composition; and, more specifically, to a grease composition favorably used in a constant velocity joint, a bearing for a continuously variable transmission, a bearing for both a car and a railway vehicle, etc.
  • the grease used in these various mechanical elements is required to suppress the temperature rise in its early stage of use from the viewpoint of extending life in particular, and reduce the friction from the viewpoints of extending life and saving energy.
  • the inventors conducted diligent studies in order to achieve the above-mentioned object and, as a result, have found that a grease composition in which specific diurea and organic molybdenum compounds are compounded at respective predetermined compounding ratios in a lubricant base oil can suppress the temperature rise in constant velocity joints, bearings for continuously variable transmissions, axle bearings for cars and railway vehicles, and the like in their early stage of use and lower the friction therein, thereby completing the present invention.
  • the grease composition in accordance with the present invention is one containing a lubricant base oil, diurea compounds represented by the following general formulas (1) to (3), and an organic molybdenum compound; wherein respective contents of the diurea compounds represented by the following general formulas (1) to (3) satisfy conditions defined by the following expressions (4) and (5); and wherein the organic molybdenum compound is contained by 0.1 to 20 mass% based on the total amount of'the grease composition: where R 1 is a hydrocarbon group containing an aromatic ring, R 2 is a divalent hydrocarbon group, and R 3 is a hydrocarbon group containing an aliphatic ring; 5 ⁇ W 1 + W 2 + W 3 ⁇ 30 0.1 ⁇ ( W 1 + 0.5 ⁇ W 2 )/( W 1 + W 2 + W 3 ) ⁇ 1.0 where W 1 , W 2 , and W 3 are respective contents (each expressed by the unit of mass%) of the diurea compounds represented by general formulas (1) to (3) based on the total amount of
  • Figs. 1A and 1B are perspective and top plan views showing a test piece used in a friction test, respectively.
  • Examples of the lubricant base oil used in the grease composition of the present invention are mineral oils and/or synthetic oils.
  • mineral oils are those obtained by a method usually carried out in a lubricant manufacturing process in a petroleum refining industry, more specifically, those obtained when a lubricant fraction yielded by distilling a crude oil under normal pressure and under reduced pressure is refined by carrying out at least one of processes of solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, contact dewaxing, hydro-refining, washing with sulfuric acid, clay treatment, etc.
  • the synthetic oils include poly ⁇ -olefins such as polybutene, 1-octene oligomer, and 1-decene oligomer or their hydrogenated products; diesters such as ditridecyl glutarate, di(2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, and di (3-ethylhexyl) sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, and pentaerythritol pelargonate; aromatic ester oils such as trioctyl trimellitate, tridecyl trimellitate, and tetraoctyl pyromellitate; complex esters which are esters formed by a mixed fatty acid of a dibasic acid and a monobasic acid
  • the kinetic viscosity of the lubricant base oil at 100°C is preferably 2 to 40 mm 2 /s, more preferably 3 to 20 mm 2 /s.
  • the viscosity index of the base oil is preferably at least 90, more preferably at least 100.
  • diurea compounds represented by the following general formulas (1) to (3) are added as a thickener to the lubricant base oil:
  • R 1 is a hydrocarbon group containing an aromatic ring.
  • examples of such a group include phenyl group, naphthyl group, alkylaryl groups in which at least one alkyl group is added to these groups as a substituent, and arylalkyl groups in which aryl groups such as phenyl and naphthyl groups are added to alkyl groups as substituents.
  • the number of carbons in the hydrocarbon group containing an aromatic ring represented by R 1 is not limited in particular, one with a carbon number of 7 to 12 is preferably used.
  • Specific examples of the hydrocarbon group containing an aromatic ring with such a carbon number include toluyl group, xylyl group, ⁇ -phenacyl group, t-butylphenyl group, dodecylphenyl group, benzyl group, and methylbenzyl group.
  • R 2 in general formulas (1) to (3) is a divalent hydrocarbon group (preferably with a carbon number of 6 to 20, a carbon number of 6 to 15 in particular).
  • a hydrocarbon group include linear or branched alkylene groups, linear or branched alkenylene groups, cycloalkylene groups, and aromatic groups.
  • ethylene group, 2,2-dimethyl-4-methylhexylene group, and groups represented by the following formulas (6) to (14) are preferred, the groups represented by the formulas (7) and (9) in particular:
  • R 3 is a hydrocarbon group containing an aliphatic ring. Though the number of carbons contained in the hydrocarbon group containing an aliphatic ring represented by R 3 is not restricted in particular, one with a carbon number of 7 to 12 is preferably used.
  • cyclohexyl group or alkylcyclohexyl group is preferably used.
  • Specific examples include methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, diethylcyclohexyl group, propylcyclohexyl group, isopropylcyclohexyl group, 1-methyl-3-propylcyclohexyl group, butylcyclohexyl group, pentylcyclohexyl group, pentylmethylcyclohexyl group, and hexylcyclohexyl group, among which cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, and ethylcyclohexyl group are more preferable.
  • the respective contents of the diurea compounds represented by general formulas (1) to (3) are required to satisfy the conditions represented by the following expressions (4) and (5): 5 ⁇ W 1 + W 2 + W 3 ⁇ 30 0.1 ⁇ ( W 1 + 0.5 ⁇ W 2 )/( W 1 + W 2 + W 3 ) ⁇ 1.0 where W 1 , W 2 , and W 3 are respective contents (each expressed by the unit of mass%) of the diurea compounds represented by general formulas (1) to (3) based on the total amount of the grease composition.
  • the sum W 1 +W 2 +W 3 of contents of the diurea compounds represented by general formulas (1) to (3) is 5 to 30 mass% based on the total amount of the grease composition.
  • W 1 +W 2 +W 3 is preferably at least 10 mass%.
  • W 1 +W 2 +W 3 exceeds 30 mass%, the composition becomes too hard as a grease, thereby failing to exhibit a sufficient lubricating property.
  • W 1 +W 2 +W 3 is preferably 20 mass% or less.
  • (W 1 +0.5 ⁇ W 2 )/ (W 1 +W 2 +W 3 ) in expression (5) is less than 0.1, the effect of suppressing the temperature rise in the early stage of use becomes weaker.
  • (W 1 +0.5 ⁇ W 2 )/(W 1 +W 2 +W 3 ) is preferably at least 0.2, more preferably at least 0.3, further preferably at least 0.4.
  • (W 1 +0.5 ⁇ W 2 )/(W 1 +W 2 +W 3 ) is preferably not greater than 0.7, more preferably less than 0.55, further preferably less than 0.5.
  • the grease composition of the present invention is relatively less likely to harden.
  • (W 1 +0.5 ⁇ W 2 )/(W 1 +W 2 +W 3 ) is preferably at least 0.3, more preferably at least 0.35, further preferably at least 0.4, at least 0.45 in particular.
  • these diurea compounds are obtained when a diisocyanate represented by the general formula of OCN-R 2 -NCO and an amine represented by the general formula of R 1 -NH 2 and/or R 3 -NH 2 are caused to react against each other at a temperature of 10° to 200°C in the base oil.
  • R 1 , R 2 , and R 3 correspond to those of (1) to (3), respectively.
  • the diurea compounds may be a mixture of a reaction product of diisocyanate and the amine represented by R 1 -NH 2 , and a reaction product of diisocyanate and the amine represented by R 3 -NH 2 ; or a reaction product of diisocyanate and a mixture of the amine represented by R 1 -NH 2 and the amine represented by R 3 -NH 2 .
  • the grease composition of the present invention further contains an organic molybdenum compound in addition to the above-mentioned lubricant base oil and diurea compounds.
  • organic molybdenum compound examples include a phosphate or thiophosphate ester derivative represented by the following general formula. (15) and a dithiocarbamate ester derivative represented by the following general formula (16):
  • R may be identical or different, each representing a hydrocarbon group with a carbon number of at least 1; c pieces of X may be identical or different, each representing an oxygen atom or sulfur atom; and each of a, b, and c represents an integer of 1 to 6.
  • Examples of the hydrocarbon group represented by R in the above-mentioned formulas (15) and (16) include alkyl groups with a carbon number of 1 to 24, cycloalkyl groups with a carbon number of 5 to 7, alkylcycloalkyl groups with a carbon number of 6 to 11, aryl groups with a carbon number of 6 to 18, alkylaryl groups with a carbon number of 7 to 24, and arylalkyl groups with a carbon number of 7 to 12.
  • alkyl groups include methyl group, ethyl group, propyl group (including all the branched isomers thereof), pentyl group (including all the branched isomers thereof), hexyl group (including all the branched isomers thereof), heptyl group (including all the branched isomers thereof), octyl group (including all the branched isomers thereof), nonyl group (including all the branched isomers thereof), decyl group (including all the branched isomers thereof), undecyl group (including all the branched isomers thereof), dodecyl group (including all the branched isomers thereof), tridecyl group (including all the branched isomers thereof), tetradecyl group (including all the branched isomers thereof), pentadecyl group (including all the branched isomers thereof), hexadecyl group (including all the branched isomers thereof),
  • cycloalkyl groups include cyclopentyl group, cyclohexyl group, and cycloheptyl group.
  • alkylcycloalkyl groups include methylcyclopentyl group (including all the substituted isomers thereof), ethylcyclopentyl group (including all the substituted isomers thereof), dimethylcyclopentyl group (including all the substituted isomers thereof), propylcyclopentyl group (including all the branched isomers and substituted isomers thereof), methylethylcyclopentyl group (including all the substituted isomers thereof), trimethylcyclopentyl group (including all the substituted isomers thereof), butylcyclopentyl group (including all the branched isomers and substituted isomers thereof), methylpropylcyclopentyl group (including all the branched isomers and substituted isomers thereof), diethylcyclopentyl group (including all the substituted isomers thereof), dimethylcyclopentyl group (including all the substituted isomers thereof), methylcyclohexyl group (
  • aryl groups include phenyl group and naphthyl group.
  • alkylaryl groups include tolyl group (including all the substituted isomers thereof), xylyl group (including all the substituted isomers thereof), ethylphenyl group (including all the substituted isomers thereof), propylphenyl group (including all the branched isomers and substituted isomers thereof), methylethylphenyl group (including all the substituted isomers thereof), trimethylphenyl group (including all the substituted isomers thereof), butylphenyl group (including all the branched isomers and substituted isomers thereof), methylpropylphenyl group (including all the branched isomers and substituted isomers thereof), diethylphenyl group (including all the substituted isomers thereof), dimethylethylphenyl group (including all the substituted isomers thereof), pentylphenyl group (including all the branched isomers and substituted isomers thereof), hexylphen
  • arylalkyl groups examples include benzyl group, phenethyl group, phenylpropyl group (including all the branched isomers thereof), and phenylbutyl group (including all the branched isomers and substituted isomers thereof).
  • Specific examples of the compounds represented by the above-mentioned general formulas (15) and (16) include molybdenum phosphate, molybdenum thiophosphate, molybdenum dithiophosphate, and molybdenum dithiocarbamate.
  • the phosphate or thiophosphate ester derivative represented by the above-mentioned formula (15) and the dithiocarbamate ester derivative represented by the above-mentioned formula (16) are compounds usually obtained by causing a phosphate ester, a thiophosphate ester, or a dithiocarbamate ester to react with an inorganic molybdenum compound (molybdenum trioxide, molybdenum oxide, salts thereof, etc.) together with a sulfur source if necessary.
  • an inorganic molybdenum compound molybdenum trioxide, molybdenum oxide, salts thereof, etc.
  • the respective compounds represented by the above-mentioned general formulas (15) and (16) may be used separately or in a mixture.
  • the compound represented by the above-mentioned general formula (16) is more preferable because of its better thermal stability.
  • the content of the organic molybdenum compound in the present invention is at least 0.1 mass%, preferably at least 0.5 mass%, based on the total amount of the grease composition. On the other hand, the content is not greater than 20 mass%, preferably not greater than 10 mass%.
  • the friction reducing effect of the grease is insufficient when the content of the organic molybdenum compound is less than 0.1 mass%, whereas the friction reducing effect cannot be obtained in proportion to the amount of addition when the content exceeds 20 mass%.
  • At least one species of compound selected from the group consisting of paraffin oxides and phosphorus compounds is added to the grease composition of the present invention.
  • these compounds are added, a higher level of resistance to fretting can be achieved over a long period in a constant velocity joint in which micromotion wear (fretting) is likely to become problematic upon minute reciprocation in particular.
  • paraffin oxides used in the present invention include paraffin oxide, salts of paraffin oxide, and esters of paraffin oxide.
  • paraffin oxide mentioned here include those obtained by oxidizing petroleum waxes such as paraffin wax, microcrystalline wax, and slack wax, or a synthetic wax such as polyolefin wax.
  • the salts of paraffin oxide include alkali metal salts, alkaline earth metal salts, and amine salts of paraffin oxide.
  • esters of paraffin oxide include esters formed between an alcohol (most preferably methanol) having a carbon number of 1 to 24 (preferably 1 to 12, more preferably 1 to 6) and paraffin oxide.
  • the paraffin oxides used in the present invention may have any properties.
  • their melting point is preferably at least 25°C, more preferably 30°C, but preferably not higher than 110°C, more preferably not higher than 70°C.
  • the total acid number is preferably at least 0.2 mgKOH/g, more preferably at least 1 mgKOH/g, but preferably not greater than 65 mgKOH/g, more preferably not greater than 40 mgKOH/g.
  • phosphorus compounds include phosphate esters, acid phosphate esters, amine salts of acid phosphate esters, chlorinated phosphate esters, phosphite esters, and thiophosphate esters. These phosphorus compounds are esters formed between phosphoric acid, phosphorous acid, or thiophosphoric acid and an alkanol or polyether alcohol, or their derivatives.
  • phosphate esters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, and xylenyldiphenyl phosphate.
  • Examples of the acid phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphat
  • amine salts of acid phosphate esters include salts formed between the acid phosphate esters and amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, and trioctylamine.
  • amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibut
  • chlorinated phosphate esters examples include tris(dichloropropyl)phosphate, tris(chloroethyl)phosphate, tris(chlorophenyl)phosphate, and polyoxyalkylene bis[di(chloroalkyl)]phosphate.
  • phosphite esters examples include phosphite diesters such as dibutyl hydrogen phosphite, dipentyl hydrogen phosphite, dihexyl hydrogen phosphite, diheptyl hydrogen phosphite, dioctyl hydrogen phosphite, dinonyl hydrogen phosphite, didecyl hydrogen phosphite, diundecyl hydrogen phosphite, didodecyl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, and dicresyl hydrogen phosphite; and phosphite triesters such as tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl
  • phosphorothionate examples include tributyl phosphorothionate, tripentyl phosphorothionate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl phosphorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate, triheptadecyl phosphorothionate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothionate, trixylenyl phosphorothionate, cres
  • the above-mentioned phosphorus compounds may be used one by one or in a mixture of two or more.
  • phosphite esters are preferable, phosphite diesters are more preferable, and diphenyl hydrogen phosphite is further preferable.
  • the content of at least one compound selected from the group consisting of the paraffin oxides and phosphorus compounds is preferably at least 0.5 mass%, more preferably at least 1.0 mass%, based on the total amount of the grease composition.
  • the content is preferably not greater than 15 mass%, more preferably 10 mass%.
  • the content exceeds 15 mass%, the resistance to fretting cannot be obtained in proportion to the amount of addition.
  • (W 1 +0.5 ⁇ W 2 )/(W 1 +W 2 +W 3 ) in expression (5) is preferably at least 0.3, more preferably at least 0.35, further preferably at least 0.4, furthermore preferably at least 0.45, but is preferably not greater than 0.7, more preferably not greater than 0.6, further preferably less than 0.5.
  • the grease composition of the present invention can further contain solid lubricants, extreme pressure agents, antioxidants, oily agents, antirusts, viscosity index improvers, etc. when necessary as long as its properties do not deteriorate.
  • solid lubricants include graphite, graphite fluoride, polytetrafluoroethylene, molybdenum disulfide, antimony sulfide, and alkali (earth) metal borates.
  • extreme pressure agents include organic zinc compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate; and sulfur-containing compounds such as dihydrocarbyl polysulfide, sulfide esters, thiazole compounds, and thiadiazole compounds.
  • antioxidants include phenol type compounds such as 2,6-di-t-butylphenol and 2,6-di-t-butyl-p-cresol; amine type compounds such as dialkyldiphenylamine, phenyl- ⁇ -naphthylamine, and p-alkylphenyl- ⁇ -naphthylamine; sulfur type compounds; and phenothiazine type compounds.
  • oily agents include amines such as laurylamine, myristylamine, palmitylamine, stearylamine, and oleylamine; higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid; fatty acid esters such as methyl laurate, methyl myristate, methyl palmitate, methyl stearate, and methyl oleate; amides such as laurylamide, myristylamide, palmitylamide, stearylamide, and oleylamide; and fats and oils.
  • amines such as laurylamine, myristylamine, palmitylamine, stearylamine, and oleylamine
  • higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol
  • antirusts include metal soaps; polyhydric alcohol partial esters such as sorbitan fatty acid esters; amines; phosphoric acid; and phosphates.
  • viscosity index improvers include polymethacrylate, polyisobutylene, and polystyrene.
  • the grease composition of the present invention can be prepared, for example, by mixing and stirring the diurea compounds represented by general formulas (1) to (3) and an organic molybdenum compound, together with other additives if necessary, with a lubricant base oil; and passing thus obtained mixture through a roll mill or the like.
  • the grease composition can also be made by adding the material components of the diurea compounds represented by general formulas (1) to (3) to the lubricant base oil beforehand; melting them together; stirring and mixing them so as to prepare the diurea compounds; then mixing and stirring them with the organic molybdenum compound, together with other additives if necessary; and passing thus obtained mixture through a roll mill or the like.
  • the grease composition of the present invention is excellent in suppressing temperature rises and reducing friction, and thus is useful as a grease for various gears of constant velocity joints, constant velocity gears, and transmission gears, and various bearings such as ball bearings and roller bearings, and is favorably used in constant velocity joints, bearings for continuously variable transmissions, gears and bearings for ironmaking equipment, axle bearings for cars/railway vehicles, etc. in particular.
  • diphenylmethane-4,4'-diisocyanate (MDI) was dissolved into the base oil by heating, and monoamines listed in Tables 1 and 2, each dissolved in the base oil, were added thereto.
  • Various additives listed in the following were added to thus generated gel-like materials, so as to yield the compositions shown in Tables 1 and 2, and after stirring, the resulting mixtures were passed through a roll mill, so as to yield the grease compositions of Examples 1 to 7 and Comparative Examples 1 to 5.
  • Figs. 1A and 1B are perspective and top plan views showing a test piece used in a friction test, respectively.
  • a needle holder 2 14 mm ⁇ 10 mm ⁇ 2.5 mm
  • a lower disc 1 24 mm in diameter ⁇ 7.9 mm
  • three' needles (each having a size of 3 mm in diameter ⁇ 13.8 mm) were accommodated in the needle holder 2, and an upper disc 4 (20 mm in diameter ⁇ 13 mm) was disposed thereon.
  • test pieces were set in an SRV friction tester such that the angle ⁇ [deg] (needle set angle) formed between a line l 1 , perpendicular to sliding directions of the upper disc 4, passing the center O of the upper face of the lower disc 1 and a line l 2 , parallel to the longitudinal direction of the needle 3, passing the center O became 30 deg, and a friction test was carried out under a condition with a frequency of 40 Hz, an amplitude of 3 mm, a load of 1000 N, and a temperature of 80°C. Table 1 and 2 show the respective friction coefficients obtained 10 minutes thereafter when using the individual grease compositions.
  • the grease composition of the present invention can realize, at a high level, the suppression of the temperature rise in the early stage of use and the reduction of the friction.

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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)
EP03719158A 2002-04-26 2003-04-22 Schmiermittelzusammensetzung Withdrawn EP1500693A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002127125 2002-04-26
JP2002127125A JP2003321692A (ja) 2002-04-26 2002-04-26 グリース組成物
PCT/JP2003/005114 WO2003091367A1 (fr) 2002-04-26 2003-04-22 Composition de graisse

Publications (2)

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EP1500693A1 true EP1500693A1 (de) 2005-01-26
EP1500693A4 EP1500693A4 (de) 2006-03-22

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US (1) US20060052257A1 (de)
EP (1) EP1500693A4 (de)
JP (1) JP2003321692A (de)
AU (1) AU2003235354A1 (de)
WO (1) WO2003091367A1 (de)

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EP1559771A1 (de) * 2002-07-24 2005-08-03 Nippon Oil Corporation Schmiermittelzusammensetzung
EP1666575A1 (de) * 2004-12-03 2006-06-07 Ab Skf Verwendung eines Schmierfettes zur Verringerung von Fressverschleiss
EP1719812A1 (de) * 2004-02-09 2006-11-08 Ntn Corporation Schmierfett, wälzlager, doppelgelenk und rollende teile
EP1801192A1 (de) * 2004-09-07 2007-06-27 Ntn Corporation Schmierfettzusammensetzung für autoradlager
EP2612899A4 (de) * 2010-09-02 2015-09-16 Kyodo Yushi Schmierfettzusammensetzung für ein lager einer nabeneinheit

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JP4937531B2 (ja) * 2005-06-09 2012-05-23 Ｎｔｎ株式会社 ハブベアリング
JP5165887B2 (ja) 2006-12-28 2013-03-21 協同油脂株式会社 等速ジョイント用グリース組成物及び等速ジョイント
JP5108315B2 (ja) * 2007-02-01 2012-12-26 昭和シェル石油株式会社 有機モリブデン化合物よりなる摩擦調整剤およびそれを含む潤滑組成物
JP5108316B2 (ja) * 2007-02-01 2012-12-26 昭和シェル石油株式会社 有機モリブデン化合物よりなる摩擦調整剤およびそれを含む潤滑組成物
JP5350597B2 (ja) * 2007-03-26 2013-11-27 協同油脂株式会社 グリース組成物及び機械部品
EP2617803B1 (de) * 2010-09-13 2018-03-21 NTN Corporation Schmierfettzusammensetzung und kugellager
JP5335019B2 (ja) * 2011-03-07 2013-11-06 Ｎｔｎ株式会社 自動車車輪軸受用グリース組成物
CN103097504B (zh) * 2011-08-26 2014-06-18 日本精工株式会社 润滑脂组合物和滚动装置
CN104312676A (zh) * 2014-09-11 2015-01-28 东莞市唯能润滑科技有限公司 一种陶瓷阀芯润滑脂及其制备方法
DE112016002660T5 (de) * 2015-06-12 2018-05-24 Jtekt Corporation Schmierfettzusammensetzung und Wälzvorrichtung für ein Fahrzeug
CN114555764B (zh) * 2019-09-24 2023-10-03 株式会社捷太格特 润滑脂组合物和滚动轴承

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EP1559771A1 (de) * 2002-07-24 2005-08-03 Nippon Oil Corporation Schmiermittelzusammensetzung
EP1559771A4 (de) * 2002-07-24 2007-02-14 Nippon Oil Corp Schmiermittelzusammensetzung
EP1719812A1 (de) * 2004-02-09 2006-11-08 Ntn Corporation Schmierfett, wälzlager, doppelgelenk und rollende teile
EP1719812A4 (de) * 2004-02-09 2012-05-23 Ntn Toyo Bearing Co Ltd Schmierfett, wälzlager, doppelgelenk und rollende teile
EP1801192A1 (de) * 2004-09-07 2007-06-27 Ntn Corporation Schmierfettzusammensetzung für autoradlager
EP1801192A4 (de) * 2004-09-07 2013-01-02 Ntn Toyo Bearing Co Ltd Schmierfettzusammensetzung für autoradlager
EP1666575A1 (de) * 2004-12-03 2006-06-07 Ab Skf Verwendung eines Schmierfettes zur Verringerung von Fressverschleiss
WO2006058637A1 (en) * 2004-12-03 2006-06-08 Ab Skf Use of a lubricant
EP2612899A4 (de) * 2010-09-02 2015-09-16 Kyodo Yushi Schmierfettzusammensetzung für ein lager einer nabeneinheit

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US20060052257A1 (en) 2006-03-09
AU2003235354A1 (en) 2003-11-10
JP2003321692A (ja) 2003-11-14
WO2003091367A1 (fr) 2003-11-06
EP1500693A4 (de) 2006-03-22

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