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WO2003091367A1 - Composition de graisse - Google Patents

Composition de graisse Download PDF

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Publication number
WO2003091367A1
WO2003091367A1 PCT/JP2003/005114 JP0305114W WO03091367A1 WO 2003091367 A1 WO2003091367 A1 WO 2003091367A1 JP 0305114 W JP0305114 W JP 0305114W WO 03091367 A1 WO03091367 A1 WO 03091367A1
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WO
WIPO (PCT)
Prior art keywords
group
phosphate
isomers
grease composition
branched
Prior art date
Application number
PCT/JP2003/005114
Other languages
English (en)
Japanese (ja)
Inventor
Hirotsugu Kinoshita
Souichi Nomura
Takashi Arai
Kiyomi Sakamoto
Original Assignee
Nippon Oil Corporation
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
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to US10/512,575 priority Critical patent/US20060052257A1/en
Priority to AU2003235354A priority patent/AU2003235354A1/en
Priority to EP03719158A priority patent/EP1500693A4/fr
Publication of WO2003091367A1 publication Critical patent/WO2003091367A1/fr

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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 particularly, to a grease composition suitably used for constant velocity joints, bearings for continuously variable transmissions, bearings for automobiles and railway vehicles, and the like.
  • Lubricants are used for various mechanical parts where metals come into contact with each other, such as constant velocity joints for transmitting driving force from the mission of automobiles to tires, bearings for continuously variable transmissions such as automobiles, and axle bearings for automobiles and railway vehicles. As grease.
  • the grease used for these various mechanical parts is required to suppress the temperature rise, especially at the beginning of use, from the viewpoint of extending the life, and to reduce the friction from the viewpoint of extending the life and saving energy.
  • the present invention has been made in view of the above-mentioned problems of the related art, and an object of the present invention is to provide a grease composition capable of suppressing a rise in temperature in an early stage of use and reducing friction at a high level.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, a grease composition in which a specific diurea compound and an organic molybdenum compound are blended in a lubricating base oil in a predetermined blending ratio, respectively, has a constant velocity joint.
  • the present inventors have found that bearings for stepped transmissions, bearings for axles for automobiles and railway vehicles, suppress the temperature rise in the initial stage of use and reduce friction, and have completed the present invention.
  • the grease composition of the present invention contains a lubricating base oil, a diurea compound represented by the following general formulas (1) to (3), and an organic molybdenum compound, and the following general formula (1) to (
  • the content of each of the diurea compounds represented by 3) satisfies the conditions represented by the following formulas (4) and (5), and the content of the organic molybdenum compound is 0.1 to 20 based on the total amount of the grease composition. % By mass.
  • R 1 represents an aromatic ring-containing hydrocarbon group
  • R 2 represents a divalent hydrocarbon group
  • R 3 represents an alicyclic ring-containing hydrocarbon group.
  • W 2 and W 3 are the content ratios of the diurea compounds represented by the general formulas (1) to (3), respectively, based on the total amount of the grease composition. % By mass). ]
  • 1A and 1B are a perspective view and a top view showing a test piece used for a friction test, respectively.
  • the lubricating base oil used in the grease composition of the present invention includes mineral oil and z or synthetic oil.
  • mineral oils examples include those obtained by a method usually used in a lubricating oil production process in the petroleum refining industry, and more specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation.
  • polybutene Specific examples of the synthetic oils, 1-OTA Ten oligomer, 1 over de Sen'ori sesame Chief of Helsingborg a Orefin or hydrides thereof; Jitorideshirugu Rutareto, Kishiruaji Bae over preparative to di-2 Echiru, Jiisodeshiruaji base one DOO Diesters such as dito-V-decyl adipate and di-3-ethylhexyl sebacate; trimethylolpropane caprylate, trimethylolpropaneperargonate, pentaerythritol, 2-ethylinohexanoate, and pentaerythri tonoleperanoregone Polyesters such as phosphates; Aromatic ester oils such as trioctyl trimellilate, tridecyl trimellilate, and tetraoctyl viromellitate; Complexes that are esters of mixed fatty acids of dibasic acids and monobasic acids
  • the kinematic viscosity at 100 ° C. of these lubricating base oils is preferably 2 to 40 mm 2 / s, more preferably 3 to 2 Omm 2 / s.
  • the viscosity index of the base oil is preferably 90 or more, and more preferably 100 or more.
  • the diurea compounds represented by the following general formulas (1) to (3) are added to the lubricating base oil as a thickener. o o
  • R 1 represents an aromatic ring-containing hydrocarbon group.
  • examples of such a group include a phenyl group, a naphthyl group, and an alkylaryl group in which these groups are substituted with one or more alkyl groups, and an aryl group such as a phenyl group and a naphthyl group. And an arylalkyl group substituted with a group.
  • the number of carbon atoms in the aromatic ring-containing hydrocarbon group represented by R 1 is not particularly limited, but those having 7 to 12 carbon atoms are preferably used.
  • Specific examples of the aromatic ring-containing hydrocarbon group having such a carbon number include a tolyl group, a xylyl group, a monophensyl group, a t-butylphenyl group, a dodecylphenyl group, a benzinole group, a methylbenzyl group, and the like.
  • R 2 in the general formulas (1) to (3) represents a divalent hydrocarbon group (preferably a divalent hydrocarbon group having 6 to 20, and particularly preferably 6 to 15 carbon atoms).
  • a hydrocarbon group include a linear or branched alkylene group, a linear or branched alkenylene group, a cycloalkylene group, and an aromatic group.
  • an ethylene group, a 2,2-dimethyl-4-methylhexylene group and groups represented by the following formulas (6) to (14) are preferable, and groups represented by the formulas (7) and (9) are preferable. Particularly preferred.
  • R 3 represents an alicyclic ring-containing hydrocarbon group.
  • the number of carbon atoms of the alicyclic ring-containing hydrocarbon group represented by R 3 is not particularly limited, but those having 7 to 12 are preferably used.
  • a cyclohexyl group or an alkylcyclohexyl group is preferably used as the alicyclic ring-containing hydrocarbon group represented by R 3 .
  • the content ratio of each of the diurea compounds represented by the general formulas (1) to (3) needs to satisfy the conditions represented by the following formulas (4) and (5).
  • W 2 and W 3 are the content ratios of the diurea compounds represented by the general formulas (1) to (3) based on the total amount of the grease composition. % By mass). ]
  • the sum of the content of the diurea compounds represented by the general formulas (1) to (3) + W 2 + W 3 is 5 to 30% by mass based on the total amount of the grease composition. so is there. If Wi + Ws + Ws is less than 5% by mass, the effect as a thickening agent is small and the grease will not be sufficient, for the same reason. Is preferably 10% by mass or more. On the other hand, if Wi + Ws + Wg exceeds 30% by mass, the grease becomes too hard to exhibit sufficient lubrication performance, and for the same reason, it is ⁇ + Ws + W ⁇ S 0 mass. / 0 or less is preferable.
  • (W x +0.5 XW 2 ) / (W x + W 2 + W3) is preferably 0.2 or more, more preferably 0.3 or more, and 0.4 or more. Is more preferable.
  • + 5 XW 2) / ( W ⁇ W ⁇ Wa) is preferably is 0.7 or less, more preferably that it is a less than 0.55 , More preferably less than 0.5.
  • the urea thickening agent generally has the property of becoming hard with time, but the grease composition of the present invention is relatively hard to harden.
  • (W + 0.5 XW 2 ) / (W x + W 2 + W 3 ) in the equation (5) is preferably 0.3 or more because it becomes harder to harden. It is more preferably at least, more preferably at least 0.4, particularly preferably at least 0.45.
  • diurea compounds include, for example, a diisocyanate represented by the general formula OCN—R 2 —NCO and an amine represented by the general formula R 1 —NH 2 and / or R 3 —NH 2 in a base oil. 0-200. It is obtained by reacting with C. At this time, RR 2 and R 3 correspond to R 1 R 2 and R 3 in the general formulas (1) to (3).
  • the grease composition of the present invention further contains an organic molybdenum compound in addition to the lubricating base oil and the diurea compound.
  • organic molybdenum compound examples include a derivative of phosphoric acid or thiophosphoric acid ester represented by the following general formula (15), and a derivative of a dithiopotamyl ester represented by the following general formula (16). .
  • R may be the same or different, each represents a hydrocarbon group having 1 or more carbon atoms, and c Xs may be the same or different, Each represents an oxygen atom or a sulfur atom, and a, b, and c each represent an integer of 1 to 6.
  • examples of the hydrocarbon group represented by R include an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and a carbon atom having 6 to 11 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group (including all branched isomers), a butyl group (including all branched isomers), a pentyl group (including all branched isomers).
  • cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • alkylcycloalkyl group examples include a methylcyclopentyl group (including all substituted isomers), an ethylcyclopentyl group (including all substituted isomers), and a dimethylcyclopentyl group (including all substituted isomers).
  • Protyl cyclopentyl group (including all branched and substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (including all substituted isomers) ), Butylcyclopentyl group (including all branched and substituted isomers), methylpropyl cyclopentyl group (including all branched and substituted isomers), getylcyclopentyl group (including all substituted isomers) ), Dimethylethyl pentyl group (including all substituted isomers), Hexyl group (including all substituted isomers), ethyl-hexyl group (including all substituted isomers), dimethyl-cycle hexyl group (including all substituted isomers), propyl-cycle hexyl Group (including all branched isomers and substituted isomers), methylethylcyclohexyl group (including all substituted isomers), tri
  • aryl group examples include a phenyl group and a naphthyl group.
  • alkylaryl group examples include a tolyl group (including all substituted isomers), a xylyl group (including all substituted isomers), and an ethylfuryl group (including all substituted isomers). ), Propylfuryl group (including all branched and substituted isomers), methylethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers) , Butylphenyl group (including all branched isomers and substituted isomers), methylpropylphenyl group (including all branched isomers and substituted isomers), getylphenyl group (including all substituted isomers) , Dimethylethyl phenyl group (including all substituted isomers), pentylphenyl group (including all branched isomers and substituted isomers), hexylphenyl group (including all branched isomers) Isomers, substituted
  • arylalkyl group examples include a benzyl group, a phenethyl group, a phenylpropyl group (including all branched isomers), and a phenylbutyl group (including all branched isomers).
  • Specific examples of the compounds represented by the general formulas (15) and (16) include molybdenum phosphate, molybdenum thiophosphate, molybdenum dithiophosphate, molybdenum dithiocarbamate, and the like.
  • Phosphoric acid or thiophosphoric acid ester derivatives represented by the following general formula (15) and dithiol rubamic acid ester derivatives represented by the following general formula (16) are usually phosphoric acid esters or thiophosphoric acid esters. It is a compound obtained by reacting dithiocarbamic acid ester with an inorganic molybdenum compound (molybdenum trioxide, molybdic acid or a salt thereof), if necessary, together with a sulfur source.
  • an inorganic molybdenum compound molybdenum trioxide, molybdic acid or a salt thereof
  • the compound obtained by the above reaction is a mixture.
  • the most typical compounds include compounds represented by the following formulas (17) and (18).
  • the organic molybdenum compound in the present invention only the compound represented by the general formula (15) may be used, or only the compound represented by the general formula (16) may be used. However, both may be used as a mixture. However, when used as a ballast for bearings, the compound represented by the above general formula (16) is preferable because of its superior thermal stability.
  • the content ratio of the organic molybdenum compound in the present invention is 0.1% by mass or more, preferably 0.5% by mass / 0 or more based on the total amount of the Darryce composition.
  • the content is 20% by mass or less, preferably 10% by mass or less.
  • the grease composition of the present invention in order to improve fretting resistance, it is preferable to mix one or more compounds selected from the group consisting of paraffin oxides and phosphorus compounds. When these compounds are blended, a higher level of fretting resistance can be achieved over a long period of time, particularly in constant velocity joints in which fine movement wear (fretting) is likely to be a problem due to minute reciprocating movement.
  • Examples of the oxidized paraffin used in the present invention include oxidized paraffin, oxidized paraffin salts, and oxidized paraffin esters.
  • oxidized paraffin mentioned here, no. Examples thereof include those obtained by oxidizing petroleum waxes such as raffin wax, microcrystalline wax and slack wax, and synthetic waxes such as polyolefin wax.
  • the salt of paraffin oxide include alkali metal salts, alkaline earth metal salts, and amine salts of the above paraffin oxide. I can do it.
  • Examples of the ester of oxidized paraffin include an ester of an alcohol (most preferably methanol) having 1 to 24 (preferably 1 to 12, more preferably 1 to 6) carbon atoms and the above paraffin oxide.
  • the melting point is preferably 25 ° C or higher, more preferably 30 ° C, and preferably 110 ° C. It is below 70 ° C, more preferably below 70 ° C.
  • the total acid value is preferably at least 0.2 mg KOH / g, more preferably at least 1 mg KOH / g, and at most 65 mg KOHZg, more preferably at most 40 mg KOH / g.
  • the phosphorus compound examples include a phosphoric acid ester, an acidic phosphoric acid ester, an amine salt of an acidic phosphoric acid ester, a chlorinated phosphoric acid ester, a phosphite, and a thiophosphoric acid ester.
  • These phosphorus compounds are esters of phosphoric acid, phosphorous acid or thiophosphoric acid with alkanols, polyether alcohols or derivatives thereof.
  • the phosphoric acid esters include tributyl phosphate, tripentinole phosphate, trihexyl phosphate, triheptinole phosphate, tri-octinole phosphate, trinoel phosphate, and tridecino.
  • Rephosphate tridecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecinolephosphate, trihexadecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, trioctadecyl phosphate , Trioleyl phosphate, triphenyl phosphate, tricresinole phosphate, trixyleninole phosphate, cresinole diphenyl phosphate, xylenyl diphenyl phosphate and the like. It is.
  • Examples of the acidic phosphoric acid ester include monobutyl acid phosphate, monopentinoleic acid phosphate, monohexinoleic acid phosphate, monoheptyl acid phosphate, monooctinoleic acid phosphate, monononinoleic acid phosphate, monodecinoleic acid phosphate, Monoundecyl acid phos Fate, monododecylacid phosphate, monotridecylacid phosphate, monotetradecylacid phosphate, monopentadecylacid phosphate, monohexadecinoleate acid phosphate, monoheptadecyl acid phosphate, monoacid acid phosphate.
  • Examples of the acid phosphate ester amine salt include the above-mentioned acid phosphate methylamine, ethylamine, propynoleamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine.
  • chlorinated phosphoric acid ester examples include tris'dichloropropyl phosphate, tris'chloroethynolephosphate, tris.chlorophenophosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like.
  • phosphites include dibutyl hydrogen phosphite, dipentyl hydrogen phosphite, dihexyl hydrogen phosphite, diheptinol hydrogen phosphite, dioctinole hydrogen phosphite, and dinoninoleno.
  • Phosphorothionates include tributylphosphorochonate, tripentinolephosphorochonate, trihexynolefosfolotionate, triheptinolephosphorochonate, trioctinolephosphorochonate, and trinonylphosphonate.
  • Tridecinolephosphorochonate Tridindecylphosphorochonate, Tridodecylphosphorochonate, Tritridecylphosphorochonate, Tritetradecylphosphorochonate, Tripentadecinophorosphorotionate Nitrate, trihexadecinolephosphorotionate, triheptadecinolephosphorochonate, trioctadecylphosphorochonate, trioleylphosphorochonate, triffe Binorefosfolonate, Tricresinolefofofonate, Trixyleninolefosfofonate, Cresinoresifenorenofofofonate, Xyleninores phen-norefosfofonate, Tris (n-propinolephenyl) phosphorofonate Enil) Phosphorothionate, Tris (n-butynolephenol) Phosphorotionate, Tris (Isoptinolephenyl
  • One of the above phosphorus compounds may be used alone, or two or more thereof may be used in combination. Of these, phosphites are preferred, phosphite diesters are more preferred, and diphenylhydrogen phosphites are even more preferred, because they are more excellent in fretting resistance.
  • the content of one or more compounds selected from the group consisting of oxidized paraffins and phosphorus compounds is preferably 0.5 mass based on the total amount of the grease composition. / 0 or more, more preferably 1.0% by mass or more. If the content is less than 0.5% by mass, the fretting resistance of the grease tends to be insufficient.
  • the content ratio is preferably 15% by mass or less, more preferably 10% by mass. If the content ratio exceeds 15% by mass, fretting resistance cannot be obtained in proportion to the added amount.
  • (W 1 +0.5 XW 2 ) / + Wg) is preferably ⁇ .3 or more, more preferably 0.35 or more, still more preferably 0.4 or more, even more preferably 0.45 or more, Further, it is preferably 0.7 or less, more preferably 0.6 or less, and even more preferably less than 0.5.
  • solid lubricants In the grease composition of the present invention, solid lubricants, extreme pressure agents, antioxidants, oil agents, rust inhibitors, A viscosity index improver or the like can be contained.
  • solid lubricant examples include graphite, graphite fluoride, polytetrafluoroethylene, molybdenum disulfide, antimony sulfide, and alkali (earth) metal borate.
  • the extreme pressure agent include organic zinc compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate; sulfur-containing compounds such as dihydrocarbyl polysulfide, sulfurating ester, thiazole compound, and thiadiazole compound. And the like.
  • Specific examples of the antioxidant include phenolic compounds such as 2,6-di-t-butylphenol and 2,6-di-t-butyl-p-cresol; dialkyldiphenylenoamine, phenyl- ⁇ -naphthylamine, and ⁇ -a. Examples include amine compounds such as nolequinolefeninolehina phthylamine; sulfur compounds; phenothiazine compounds.
  • oil decaying agent examples include amines such as laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, etc .; Higher alcohols such as oleic acid, oleyl alcohol; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid; methyl laurate, methyl myristate, methyl palmitate, methyl stearate, oleic acid Fatty acid esters such as methyl; amides such as lauryl amide, myristinoleamide, palmityl amide, stearyl amide and oleyl amide; oils and fats.
  • amines such as laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, etc .
  • Higher alcohols such as oleic acid, oleyl alcohol
  • higher fatty acids such as lauric acid, myristic acid, palmi
  • stopping agent examples include metal soaps; polyhydric alcohol partial esters such as sorbitan fatty acid esters; amines; phosphoric acid; and phosphates.
  • viscosity index improver examples include polymethacrylate, polyisobutylene, and polystyrene.
  • a lubricating base oil may be prepared by adding a compound represented by the general formula (1)
  • the grease composition of the present invention is excellent in suppressing temperature rise and reducing friction, grease for various gears for constant velocity joints, constant velocity gears, transmission gears, and various bearings for ball bearings, roller bearings, and the like. It is particularly preferably used for constant velocity joints, bearings for continuously variable transmissions, gears and bearings for steelmaking facilities, and axle bearings for automobiles and railway vehicles.
  • MoDTC Molybdenum Dioctyl Dicarbamate
  • Mo P Molybdenum dibutyltin phosphate
  • Boron friction modifier (boric acid-based friction modifier)
  • Oxidized paraffins (Oxidized paraffin esters (esters of oxidized paraffin and methanol obtained by oxidizing slack wax, total acid value: 33 mg KOHZnig, saponification value: 130 kg KOH / g)) Zinodidrogen phosphite (diphenyl hydrogen phosphite).
  • the grease compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were subjected to the following temperature rise test and friction test.
  • Fuff ⁇ "Fretting resistance test was performed using a friction oxidation tester in accordance with ASTM D4170, and the amount of wear was measured. Thrust bearing 51204 (manufactured by Nippon Seie Co., Ltd.) The test time was 2 hours and the test temperature was room temperature, and in this test, one day after production of each grease composition was used as a sample. See Table 2. (Measurement of consistency)
  • the diurea compound represented by any of the general formulas (1) to (3) and the organic molybdenum compound are blended in the lubricating base oil in a specific blending ratio. Accordingly, it is possible to achieve a high level of suppression of temperature rise in the initial stage of use and reduction of 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)

Abstract

L'invention concerne une composition de graisse comprenant une huile de base lubrifiante, trois composés diurée, et un composé organomolybdène, les teneurs des trois composés diurée correspondant à une exigence spécifique, et la teneur du composé organomolybdène étant de 0,1 à 20 % en poids par rapport à la composition de graisse totale.
PCT/JP2003/005114 2002-04-26 2003-04-22 Composition de graisse WO2003091367A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/512,575 US20060052257A1 (en) 2002-04-26 2003-04-22 Grease composition
AU2003235354A AU2003235354A1 (en) 2002-04-26 2003-04-22 Grease composition
EP03719158A EP1500693A4 (fr) 2002-04-26 2003-04-22 Composition de graisse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002127125A JP2003321692A (ja) 2002-04-26 2002-04-26 グリース組成物
JP2002-127125 2002-04-26

Publications (1)

Publication Number Publication Date
WO2003091367A1 true WO2003091367A1 (fr) 2003-11-06

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PCT/JP2003/005114 WO2003091367A1 (fr) 2002-04-26 2003-04-22 Composition de graisse

Country Status (5)

Country Link
US (1) US20060052257A1 (fr)
EP (1) EP1500693A4 (fr)
JP (1) JP2003321692A (fr)
AU (1) AU2003235354A1 (fr)
WO (1) WO2003091367A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1666575A1 (fr) * 2004-12-03 2006-06-07 Ab Skf Utilisation d'une composition de graisse lubrifiante pour reduction de la corrosion de contact
EP1719812A4 (fr) * 2004-02-09 2012-05-23 Ntn Toyo Bearing Co Ltd Graisse, palier de roulement, joint a double cardan et pieces de roulement

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JP2004059604A (ja) * 2002-07-24 2004-02-26 Nippon Oil Corp グリース組成物
JP4776193B2 (ja) * 2004-09-07 2011-09-21 Ｎｔｎ株式会社 自動車車輪軸受用グリース組成物
JP4461000B2 (ja) * 2004-11-25 2010-05-12 本田技研工業株式会社 等速ジョイント用グリース組成物及び等速ジョイント
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
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
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
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
JP5681414B2 (ja) * 2010-09-02 2015-03-11 協同油脂株式会社 ハブユニット軸受用グリース組成物
WO2012036076A1 (fr) * 2010-09-13 2012-03-22 Ntn株式会社 Composition de graisse et roulement
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
EP2749631A4 (fr) * 2011-08-26 2014-07-23 Nsk Ltd Composition de graisse et dispositif à roulement
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
CN107636132A (zh) * 2015-06-12 2018-01-26 株式会社捷太格特 润滑脂组合物和车辆用滚动装置
WO2021060232A1 (fr) * 2019-09-24 2021-04-01 株式会社ジェイテクト Composition de graisse et palier à roulement

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JPH05230486A (ja) * 1992-02-19 1993-09-07 Kyodo Yushi Kk シリコーングリース組成物
JPH0657283A (ja) * 1992-08-05 1994-03-01 Kyodo Yushi Kk 等速ジョイント用グリース組成物
JPH0657284A (ja) * 1992-08-05 1994-03-01 Kyodo Yushi Kk 等速ジョイント用グリース組成物
EP0773280A2 (fr) * 1995-11-13 1997-05-14 Kyodo Yushi Co., Ltd. Composition de graisse pour joints homocinetiques
EP0796910A1 (fr) * 1996-03-22 1997-09-24 Kyodo Yushi Co., Ltd. Composition de graisse pour joints homocinétiques
GB2323851A (en) * 1997-03-31 1998-10-07 Kyodo Yushi Grease composition for constant velocity joints
JPH11181465A (ja) * 1997-12-22 1999-07-06 Nippon Seiko Kk グリース組成物
US6352961B1 (en) * 1998-02-23 2002-03-05 Nsk Ltd. Grease composition for rolling bearing
US6355602B1 (en) * 1999-06-29 2002-03-12 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint
JP2002038177A (ja) * 2000-07-28 2002-02-06 Kyodo Yushi Co Ltd 等速ジョイント用グリース組成物
JP2002180077A (ja) * 2000-12-08 2002-06-26 Ntn Corp 潤滑剤組成物および軸受
JP2003013973A (ja) * 2001-06-28 2003-01-15 Ntn Corp 耐熱・高速・高荷重転がり軸受およびグリース組成物

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1719812A4 (fr) * 2004-02-09 2012-05-23 Ntn Toyo Bearing Co Ltd Graisse, palier de roulement, joint a double cardan et pieces de roulement
EP1666575A1 (fr) * 2004-12-03 2006-06-07 Ab Skf Utilisation d'une composition de graisse lubrifiante pour reduction de la corrosion de contact

Also Published As

Publication number Publication date
EP1500693A4 (fr) 2006-03-22
JP2003321692A (ja) 2003-11-14
US20060052257A1 (en) 2006-03-09
EP1500693A1 (fr) 2005-01-26
AU2003235354A1 (en) 2003-11-10

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