US20230416633A1 - Grease composition for constant-velocity joints - Google Patents

Grease composition for constant-velocity joints Download PDF

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Publication number
US20230416633A1
US20230416633A1 US18/252,723 US202018252723A US2023416633A1 US 20230416633 A1 US20230416633 A1 US 20230416633A1 US 202018252723 A US202018252723 A US 202018252723A US 2023416633 A1 US2023416633 A1 US 2023416633A1
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United States
Prior art keywords
mass
grease composition
composition
oil
constant
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US18/252,723
Inventor
Tadaaki KONNO
Tomohiko Yamaguchi
Jisheng E
Christoph Lindlahr
Joachim Wette
Tomio Seki
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GKN Driveline International GmbH
Kyodo Yushi Co Ltd
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GKN Driveline International GmbH
Kyodo Yushi Co Ltd
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Application filed by GKN Driveline International GmbH, Kyodo Yushi Co Ltd filed Critical GKN Driveline International GmbH
Assigned to GKN DRIVELINE INTERNATIONAL GMBH, KYODO YUSHI CO., LTD. reassignment GKN DRIVELINE INTERNATIONAL GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LINDLAHR, Christoph, WETTE, JOACHIM, E, JISHENG, KONNO, Tadaaki, SEKI, TOMIO, YAMAGUCHI, TOMOHIKO
Publication of US20230416633A1 publication Critical patent/US20230416633A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/06Mixtures of thickeners and additives
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10Sulfonic acids or derivatives thereof
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
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    • C10M141/00Lubricating 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
    • C10M141/02Lubricating 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 oxygen-containing compound
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    • C10M141/08Lubricating 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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    • C10M141/10Lubricating 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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    • C10M141/12Lubricating 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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10Amides of carbonic or haloformic acids
    • C10M2215/102Ureas; Semicarbazides; Allophanates
    • C10M2215/1026Ureas; Semicarbazides; Allophanates used as thickening material
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/045Metal containing thio derivatives
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    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52Base number [TBN]
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76Reduction of noise, shudder, or vibrations
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy

Definitions

  • the present invention relates to a grease composition for constant-velocity joints.
  • FF front-wheel-drive
  • CO2 reduction vehicle environmental measures
  • CVJ constant-velocity joints
  • a plunging type constant-velocity joint rotates at angle, and internal parts of the joint perform complicated rolling and sliding motions. During these motions, the friction of the internal parts generates sliding resistance in the axial direction, and the sliding resistance, if large, may cause vibration and noise.
  • Patent Literature 1 As greases with excellent vibration suppression performance, there have been 30 proposed a grease for constant-velocity joints (see Patent Literature 1) obtained by using a urea grease in combination with additives of molybdenum dithiocarbamate and molybdenum dithiophosphate or in combination with these organomolybdenum compounds mixed with zinc dithiophosphate; and a grease composition for constant-velocity joints comprising a base oil, a urea thickener, molybdenum dithiocarbamate, calcium sulfonate, and thiophosphate (see Patent Literature 2).
  • a grease composition for constant-velocity joints comprising: a grease composed of a base oil and a urea compound thickener; and a mixture of molybdenum dialkyldithiocarbamate, at least one of molybdenum dialkyldithiophosphate and molybdenum diaryldithiophosphate, and ashless dithiocarbamate or zinc dithiocarbamate (see Patent Literature 3), and a grease composition for constant-velocity joints comprising a base oil, a diurea thickener, molybdenum dialkyldithiocarbamate sulfide, zinc sulfonate, a sulfur-phosphorus extreme pressure agent, and vegetable fat and oil (see Patent Literature 4).
  • the present invention has an object to provide a grease composition excellent in durability even at high temperature and vibration suppression performance.
  • a base oil usable in the composition of the present invention is not particularly limited and a mineral oil and/or a synthetic oil may be used.
  • the synthetic oils include: synthetic hydrocarbon oils such as poly- ⁇ -olefin; phenyl ether oils such as pentaphenyl ether, tetraphenyl ether, monoalkyltetraphenyl ether, dialkyltetraphenyl ether, and alkyldiphenyl ether oils; alkylbenzene oils; ester oils such as monoester oils, diester oils, polyol ester oils, and aromatic ester oils; polyglycol oils; silicone oils; fluorine oils; ionic liquids, and the like.
  • a mineral oil is preferably used from the viewpoint of cost.
  • a base oil may be used in which a mineral oil as a main component is mixed with a synthetic oil.
  • the base oil in the present invention is a mixture oil of a mineral oil and a synthetic oil
  • the content of the mineral oil based on the total mass of the base oil is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 90 to 100% by mass.
  • the kinematic viscosity at 100° C. of the base oil in the present invention is preferably 5 to 30 mm 2 /s and more preferably 7 to 20 mm 2 /s.
  • the kinematic viscosity is less than 5 mm 2 /s, the durability tends to be insufficient because no oil film is formed in a constant-velocity joint.
  • the kinematic viscosity exceeds 30 mm 2 /s, the durability tends to decrease due to heat generation in the CVJ.
  • the content of the base oil based on the total mass of the composition is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass.
  • the diurea thickener usable in the present invention is expressed by the following formula (1).
  • R 2 is a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
  • tolylene diisocyanate or diphenylmethane diisocyanate are preferable and diphenylmethane diisocyanate is more preferable.
  • R 1 and R 3 which may be the same as or different from each other, are each a linear or branched alkyl group having 6 to 30 carbon atoms, an aryl group having 6 or 7 carbon atoms, or a cyclohexyl group.
  • an aliphatic diurea compound in which both of R 1 and R 3 are alkyl groups having 6 to 30 carbon atoms may be obtained through a reaction of diisocyanate and aliphatic monoamine.
  • an alicyclic aliphatic diurea compound in which one of R 1 and R 3 is an alkyl group having 6 to 30 carbon atoms and the other one is a cyclohexyl group is preferable. Since the alicyclic aliphatic diurea compound can be obtained through a reaction of diisocyanate with alicyclic monoamine and aliphatic monoamine, the alicyclic aliphatic diurea compound in fact is not only an alicyclic aliphatic diurea compound but also a mixture comprising an aliphatic diurea compound and an alicyclic diurea compound.
  • any one of R 1 and R 3 is a cyclohexyl group
  • the other one is preferably a linear alkyl group having 8 or 18 carbon atoms.
  • a ratio of the cyclohexyl group to the total of the cyclohexyl group and the alkyl group is preferably 70 to 100 mol % and more preferably 80 to 100 mol % from the viewpoint of fluidity.
  • an aliphatic diurea compound is preferable from the viewpoint of durability.
  • a diurea compound in the formula (1) in which both of R 1 and R 3 are alkyl groups having 8 to 30 carbon atoms and R 2 is diphenylmethane diisocyanate.
  • R 1 and R 3 are linear alkyl groups having 8 or 18 carbon atoms and R 2 is diphenylmethane diisocyanate.
  • the consistency of the grease composition of the present invention is preferably 250 to 400, more preferably 280 to 370, and further preferably 310 to 340.
  • the term “consistency” refers to a 60-stoke worked penetration. The consistency may be measured in accordance with JIS K2220 7.
  • the content of the thickener based on the total mass of the composition is preferably 10% by mass or less, more preferably 5 to 10% by mass, and further preferably 6 to 7% by mass such that the consistency of the grease composition can be set within the above range.
  • the molybdenum dithiocarbamate usable in the present invention is a general term for organometallic load bearing additives whose metal group is molybdenum, and is generally widely used as an extreme pressure additive.
  • a preferred example of the molybdenum dithiocarbamate can be expressed by the following formula (2).
  • the molybdenum dithiocarbamate includes oil-soluble molybdenum dithiocarbamate (that is, liquid at room temperature (about 25° C.)) and oil-insoluble molybdenum dithiocarbamate (that is, solid at room temperature).
  • oil-soluble molybdenum dithiocarbamate that is, liquid at room temperature (about 25° C.)
  • oil-insoluble molybdenum dithiocarbamate that is, solid at room temperature.
  • any of them may be used, but a combination of an oil-soluble molybdenum dithiocarbamate and an oil-insoluble molybdenum dithiocarbamate is preferable because the resultant composition is excellent in durability and heat generation suppression and vibration suppression in the CSJ.
  • the content of the component (b) based on the total mass of the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and further preferably 1 to 3% by mass from the viewpoint of vibration suppression.
  • the composition contains an oil-soluble molybdenum dithiocarbamate and an oil-insoluble molybdenum dithiocarbamate, it is preferable to use them in a mass ratio of the oil-soluble molybdenum dithiocarbamate to the oil-insoluble molybdenum dithiocarbamate of preferably 4:6 to 10:0 and more preferably 6:4 to 8:2 because the resultant composition is excellent in vibration suppression.
  • a preferred example of the molybdenum dithiophosphate used in the present invention is expressed by the following formula (3).
  • the content of the component (d) based on the total mass of the composition is preferably 0.1% by mass or more, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 2% by mass from the viewpoint of durability.
  • the overbased calcium sulfonate used in the present invention is a calcium sulfonate having a base number of 200 mgKOH/g or more.
  • the base number is preferably 300 mgKOH/g or more and more preferably 300 to 500 mgKOH/g from the viewpoint of durability.
  • the base number is a value measured in accordance with JIS K 2501.
  • a calcium salt of a sulfonic acid having a lipophilic organic group can be used.
  • organic sulfonic acids include: petroleum sulfonic acids obtained by sulfonation of aromatic hydrocarbon components in lubricating oil fractions; synthetic sulfonic acids such as dinonylnaphthalene sulfonic acid and heavy alkylbenzene sulfonic acid; and the like.
  • calcium sulfonates overbased with calcium carbonate are preferable. Above all, an alkyl aromatic calcium sulfonate containing calcium carbonate is preferable.
  • the content of the component (e) in the grease composition of the present invention based on the total mass of the composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and further preferably 1.2 to 3.5% by mass from the viewpoint of durability.
  • the neutral zinc sulfonate used in the present invention has a base number of 10 mgKOH/g or less.
  • the sulfonic acid constituting the zinc sulfonate is the same as described for the component (e).
  • neutral zinc sulfonate zinc dinonylnaphthalene sulfonate is preferable.
  • the content of the neutral zinc sulfonate in the grease composition of the present invention based on the total mass of the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and further preferably 0.8 to 3% by mass from the viewpoint of durability.
  • the total content of the components (e) and (f) based on the total mass of the composition is preferably 0.5 to 5% by mass and more preferably 1 to 3% by mass because excellent heat resistance can be obtained.
  • the grease composition of the present invention may comprise additives, which are commonly used in greases, as needed.
  • the content of these additives based on the total mass of the grease composition is usually 0.1 to 5% by mass and preferably 0.5 to 3% by mass.
  • antioxidants such as amine-based, phenol-based, quinoline-based, sulfur-based, and zinc dithiophosphate antioxidants
  • rust preventives such as zinc-based, carboxylic acid-based, carboxylate-based (especially dibasic salts of sodium sebacate, sodium azelate, sodium suberate, and the like), and amine-based rust preventives
  • anti-wear agents such as sulfurized oil and fat, sulfurized olefin, phosphate ester, phosphite ester, and acid phosphate amine salt
  • oiliness agents such as fatty acid, fatty acid ester, and phosphate ester
  • solid lubricants such as graphite, polytetrafluoroethylene (PTFE), and zinc oxide.
  • the grease composition preferably comprises an antioxidant.
  • an amine-based antioxidant is preferable and alkyl diphenylamine is more preferable.
  • the content of the antioxidant based on the total mass of the composition is preferably 0.1% by mass or more, more preferably 0.1 to 2% by mass, and further preferably 0.2 to 1% by mass.
  • composition of the present invention preferably comprises only:
  • the contents of the components in the above composition based on the total mass of the composition preferably are: (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass.
  • composition of the present invention preferably comprises:
  • the contents of the components in the above composition based on the total mass of the composition preferably are: (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass.
  • composition of the present invention preferably comprises:
  • the contents of the components in the above composition based on the total mass of the composition preferably are: (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass.
  • the grease composition of the present invention is applicable to constant-velocity joints.
  • a grease composition in Comparative Example 5 was prepared in accordance with the description of Example C4 in Japanese Patent No. 6470851.
  • the components used to prepare the grease compositions are as follows.
  • a TE77 tester is a vibration friction wear tester under sliding conditions. It has been reported that there is a relationship between vibration caused by a constant-velocity joint as a vibration source and the friction coefficient measured with the TE77 tester under vibration conditions (Japanese Patent Application Publication No. 2010-065194). Therefore, the vibration suppression in a constant-velocity joint was evaluated by using the TE77 tester.

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Abstract

The present invention provides a grease composition for constant-velocity joints comprising (a) a base oil, (b) a diurea thickener, (c) molybdenum dithiocarbamate, (d) molybdenum dithiophosphate, (e) overbased calcium sulfonate, and (f) neutral zinc sulfonate. The composition of the present invention is excellent in durability at high temperature and vibration suppression.

Description

    TECHNICAL FIELD
  • The present invention relates to a grease composition for constant-velocity joints.
  • BACKGROUND ART
  • Regarding automobiles, front-wheel-drive (FF) vehicles are widely used from the viewpoints of weight reduction for vehicle environmental measures (CO2 reduction) and securing of a living space, and constant-velocity joints (CVJ), which are essential for power transmission in FF vehicles, are widely used.
  • Among CVJ type joints, a plunging type constant-velocity joint rotates at angle, and internal parts of the joint perform complicated rolling and sliding motions. During these motions, the friction of the internal parts generates sliding resistance in the axial direction, and the sliding resistance, if large, may cause vibration and noise.
  • Along with a recent increase in the power output of automobile engines, a lubrication condition inside the constant-velocity joint has shifted to a high surface pressure condition. As the surface pressure as the lubrication condition becomes higher, wear tends to occur more easily inside the constant-velocity joint, which may cause problems such as deterioration of durability (anti-flaking property) and increase in vibration.
  • In addition, such constant-velocity joints are also required to ensure the durability at high temperature.
  • As greases with excellent vibration suppression performance, there have been 30 proposed a grease for constant-velocity joints (see Patent Literature 1) obtained by using a urea grease in combination with additives of molybdenum dithiocarbamate and molybdenum dithiophosphate or in combination with these organomolybdenum compounds mixed with zinc dithiophosphate; and a grease composition for constant-velocity joints comprising a base oil, a urea thickener, molybdenum dithiocarbamate, calcium sulfonate, and thiophosphate (see Patent Literature 2). In addition, in order to meet the recent demand for even more quietness, there have been also proposed a grease composition for constant-velocity joints comprising: a grease composed of a base oil and a urea compound thickener; and a mixture of molybdenum dialkyldithiocarbamate, at least one of molybdenum dialkyldithiophosphate and molybdenum diaryldithiophosphate, and ashless dithiocarbamate or zinc dithiocarbamate (see Patent Literature 3), and a grease composition for constant-velocity joints comprising a base oil, a diurea thickener, molybdenum dialkyldithiocarbamate sulfide, zinc sulfonate, a sulfur-phosphorus extreme pressure agent, and vegetable fat and oil (see Patent Literature 4).
  • As a grease prepared also in consideration of durability, there has been proposed a composition for constant-velocity joints comprising a base oil, a thickener, montan wax, zinc sulfonate, and molybdenum dialkyldithiocarbamate sulfide (see Patent Literature 5).
  • Thus, the grease compositions for constant-velocity joints in the related art have demonstrated excellent performance in vibration suppression, and their durability at room temperature has also been studied. On the other hand, however, it cannot be said that the problem of durability at high temperature has been sufficiently studied.
  • CITATION LIST Patent Literatures
    • Patent Literature 1: Japanese Examined Patent Application Publication No. H05-79280
    • Patent Literature 2: Japanese Patent Application Publication No. H11-172276
    • Patent Literature 3: Japanese Patent Application Publication No. 2009-235416
    • Patent Literature 4: Japanese Patent Application Publication No. 2011-37950
    • Patent Literature 5: International Publication No. WO2014/0954797
    SUMMARY OF INVENTION Problem to be Solved by the Invention
  • Therefore, the present invention has an object to provide a grease composition excellent in durability even at high temperature and vibration suppression performance.
  • Means for Solution of the Problem
      • 1. A grease composition for constant-velocity joints comprising:
        • (a) a base oil;
        • (b) a diurea thickener;
        • (c) molybdenum dithiocarbamate;
        • (d) molybdenum dithiophosphate;
        • (e) overbased calcium sulfonate; and
        • (f) neutral zinc sulfonate.
      • 2. The grease composition according to claim 1, wherein a content of the component (f) is 0.1 to 10% by mass based on the total mass of the composition.
      • 3. The grease composition according to claim 1 or 2, wherein a content of the component (f) is 0.5 to 5% by mass based on the total mass of the composition.
      • 4. The grease composition according to any one of claims 1 to 3, wherein a content of the component (f) is 0.8 to 3% by mass based on the total mass of the composition.
      • 5. The grease composition according to any one of claims 1 to 4, wherein a content of the component (e) is 0.1 to 10% by mass based on the total mass of the composition.
      • 6. The grease composition according to any one of claims 1 to 5, wherein a content of the component (e) is 0.2 to 5% by mass based on the total mass of the composition.
      • 7. The grease composition according to any one of claims 1 to 6, wherein a content of the component (e) is 1.2 to 3.5% by mass based on the total mass of the composition.
      • 8. The grease composition according to any one of claims 1 to 7, wherein the component (b) is an aliphatic diurea thickener.
      • 9. A constant-velocity joint in which the grease composition according to any one of claims 1 to 8 is enclosed.
    Advantageous Effects of Invention
  • According to the present invention, it is possible to provide a grease composition excellent in durability even at high temperature and also excellent in vibration suppression.
  • DESCRIPTION OF EMBODIMENTS (a) Base Oil
  • A base oil usable in the composition of the present invention is not particularly limited and a mineral oil and/or a synthetic oil may be used. The synthetic oils include: synthetic hydrocarbon oils such as poly-α-olefin; phenyl ether oils such as pentaphenyl ether, tetraphenyl ether, monoalkyltetraphenyl ether, dialkyltetraphenyl ether, and alkyldiphenyl ether oils; alkylbenzene oils; ester oils such as monoester oils, diester oils, polyol ester oils, and aromatic ester oils; polyglycol oils; silicone oils; fluorine oils; ionic liquids, and the like.
  • As the base oil in the present invention, a mineral oil is preferably used from the viewpoint of cost. A base oil may be used in which a mineral oil as a main component is mixed with a synthetic oil.
  • In the case where the base oil in the present invention is a mixture oil of a mineral oil and a synthetic oil, the content of the mineral oil based on the total mass of the base oil is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 90 to 100% by mass.
  • The kinematic viscosity at 100° C. of the base oil in the present invention is preferably 5 to 30 mm2/s and more preferably 7 to 20 mm2/s. When the kinematic viscosity is less than 5 mm2/s, the durability tends to be insufficient because no oil film is formed in a constant-velocity joint. When the kinematic viscosity exceeds 30 mm2/s, the durability tends to decrease due to heat generation in the CVJ.
  • From the viewpoint of the fluidity, the content of the base oil based on the total mass of the composition is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass.
  • (b) Diurea Thickener
  • The diurea thickener usable in the present invention is expressed by the following formula (1).

  • R1—NHCONH—R2—NHCONH—R3  (1)
  • In the formula, R2 is a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms. As R2, tolylene diisocyanate or diphenylmethane diisocyanate are preferable and diphenylmethane diisocyanate is more preferable. R1 and R3, which may be the same as or different from each other, are each a linear or branched alkyl group having 6 to 30 carbon atoms, an aryl group having 6 or 7 carbon atoms, or a cyclohexyl group.
  • As the diurea compound in the formula (1), an aliphatic diurea compound in which both of R1 and R3 are alkyl groups having 6 to 30 carbon atoms. The aliphatic diurea compound may be obtained through a reaction of diisocyanate and aliphatic monoamine.
  • In addition, as the diurea compound in the formula (1), an alicyclic aliphatic diurea compound in which one of R1 and R3 is an alkyl group having 6 to 30 carbon atoms and the other one is a cyclohexyl group is preferable. Since the alicyclic aliphatic diurea compound can be obtained through a reaction of diisocyanate with alicyclic monoamine and aliphatic monoamine, the alicyclic aliphatic diurea compound in fact is not only an alicyclic aliphatic diurea compound but also a mixture comprising an aliphatic diurea compound and an alicyclic diurea compound.
  • In the case where any one of R1 and R3 is a cyclohexyl group, the other one is preferably a linear alkyl group having 8 or 18 carbon atoms. In this compound, a ratio of the cyclohexyl group to the total of the cyclohexyl group and the alkyl group is preferably 70 to 100 mol % and more preferably 80 to 100 mol % from the viewpoint of fluidity.
  • As the thickener in the present invention, an aliphatic diurea compound is preferable from the viewpoint of durability.
  • In particular, preferred is a diurea compound in the formula (1) in which both of R1 and R3 are alkyl groups having 8 to 30 carbon atoms and R2 is diphenylmethane diisocyanate.
  • Above all, preferred is a diurea compound in the formula (1) in which both of R1 and R3 are linear alkyl groups having 8 or 18 carbon atoms and R2 is diphenylmethane diisocyanate.
  • The consistency of the grease composition of the present invention is preferably 250 to 400, more preferably 280 to 370, and further preferably 310 to 340. In the present specification, the term “consistency” refers to a 60-stoke worked penetration. The consistency may be measured in accordance with JIS K2220 7.
  • The content of the thickener based on the total mass of the composition is preferably 10% by mass or less, more preferably 5 to 10% by mass, and further preferably 6 to 7% by mass such that the consistency of the grease composition can be set within the above range.
  • (c) Molybdenum Dithiocarbamate (MoDTC)
  • The molybdenum dithiocarbamate usable in the present invention is a general term for organometallic load bearing additives whose metal group is molybdenum, and is generally widely used as an extreme pressure additive. A preferred example of the molybdenum dithiocarbamate can be expressed by the following formula (2).

  • [R4R5N—CS—S]2—Mo2OmSm  (2)
  • In the formula, R4 and R5, which may be the same as or different from each other, are each independently a liner or branched alkyl group having 1 to 24 carbon atoms or preferably 3 to 18 carbon atoms, m is 0 to 3, n is 4 to 1, and m+n=4.
  • The molybdenum dithiocarbamate includes oil-soluble molybdenum dithiocarbamate (that is, liquid at room temperature (about 25° C.)) and oil-insoluble molybdenum dithiocarbamate (that is, solid at room temperature). As the molybdenum dithiocarbamate in the present invention, any of them may be used, but a combination of an oil-soluble molybdenum dithiocarbamate and an oil-insoluble molybdenum dithiocarbamate is preferable because the resultant composition is excellent in durability and heat generation suppression and vibration suppression in the CSJ.
  • In the grease composition of the present invention, the content of the component (b) based on the total mass of the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and further preferably 1 to 3% by mass from the viewpoint of vibration suppression. In the case where the composition contains an oil-soluble molybdenum dithiocarbamate and an oil-insoluble molybdenum dithiocarbamate, it is preferable to use them in a mass ratio of the oil-soluble molybdenum dithiocarbamate to the oil-insoluble molybdenum dithiocarbamate of preferably 4:6 to 10:0 and more preferably 6:4 to 8:2 because the resultant composition is excellent in vibration suppression.
  • (d) Molybdenum Dithiophosphate (MoDTP)
  • A preferred example of the molybdenum dithiophosphate used in the present invention is expressed by the following formula (3).

  • [(R6O)(R7O)PS—S]2MO2OmSn
  • (In the formula, R6 and R7 are each independently an alkyl group having 1 to 24 carbon atoms or an aryl group having 6 to 30 carbon atoms, m is 0 to 3, n is 4 to 1, and m+n=4.)
  • In the grease composition of the present invention, the content of the component (d) based on the total mass of the composition is preferably 0.1% by mass or more, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 2% by mass from the viewpoint of durability.
  • (e) Overbased Calcium Sulfonate
  • The overbased calcium sulfonate used in the present invention is a calcium sulfonate having a base number of 200 mgKOH/g or more. The base number is preferably 300 mgKOH/g or more and more preferably 300 to 500 mgKOH/g from the viewpoint of durability. In the present invention, the base number is a value measured in accordance with JIS K 2501.
  • As the component (e), a calcium salt of a sulfonic acid having a lipophilic organic group can be used. Such organic sulfonic acids include: petroleum sulfonic acids obtained by sulfonation of aromatic hydrocarbon components in lubricating oil fractions; synthetic sulfonic acids such as dinonylnaphthalene sulfonic acid and heavy alkylbenzene sulfonic acid; and the like. As the component (e), calcium sulfonates overbased with calcium carbonate are preferable. Above all, an alkyl aromatic calcium sulfonate containing calcium carbonate is preferable.
  • The content of the component (e) in the grease composition of the present invention based on the total mass of the composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and further preferably 1.2 to 3.5% by mass from the viewpoint of durability.
  • (f) Neutral Zinc Sulfonate
  • The neutral zinc sulfonate used in the present invention has a base number of 10 mgKOH/g or less.
  • The sulfonic acid constituting the zinc sulfonate is the same as described for the component (e).
  • As the neutral zinc sulfonate, zinc dinonylnaphthalene sulfonate is preferable.
  • The content of the neutral zinc sulfonate in the grease composition of the present invention based on the total mass of the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and further preferably 0.8 to 3% by mass from the viewpoint of durability.
  • The total content of the components (e) and (f) based on the total mass of the composition is preferably 0.5 to 5% by mass and more preferably 1 to 3% by mass because excellent heat resistance can be obtained.
  • The mass ratio of the component (e) to the component (f) is preferably (e):(f)=9:1 to 1:9 because excellent durability can be obtained. The mass ratio is more preferably (e):(f)=8:2 to 3:7 and further preferably (e):(f)=7:3 to 4:6. In particular, it is preferable that the total content of the components (e) and (f) based on the total mass of the composition be 1 to 3% by mass and the mass ratio of the component (e) to the component (f) be (e):(f)=7:3 to 4:6, because excellent durability and heat resistance can be obtained.
  • The grease composition of the present invention may comprise additives, which are commonly used in greases, as needed. The content of these additives based on the total mass of the grease composition is usually 0.1 to 5% by mass and preferably 0.5 to 3% by mass.
  • Examples of these additives include: antioxidants such as amine-based, phenol-based, quinoline-based, sulfur-based, and zinc dithiophosphate antioxidants; rust preventives such as zinc-based, carboxylic acid-based, carboxylate-based (especially dibasic salts of sodium sebacate, sodium azelate, sodium suberate, and the like), and amine-based rust preventives; anti-wear agents such as sulfurized oil and fat, sulfurized olefin, phosphate ester, phosphite ester, and acid phosphate amine salt; oiliness agents such as fatty acid, fatty acid ester, and phosphate ester; and solid lubricants such as graphite, polytetrafluoroethylene (PTFE), and zinc oxide.
  • From the viewpoint of heat resistance, the grease composition preferably comprises an antioxidant.
  • As the antioxidant, an amine-based antioxidant is preferable and alkyl diphenylamine is more preferable. The content of the antioxidant based on the total mass of the composition is preferably 0.1% by mass or more, more preferably 0.1 to 2% by mass, and further preferably 0.2 to 1% by mass.
  • The composition of the present invention preferably comprises only:
      • (a) a base oil;
      • (b) a diurea thickener;
      • (c) molybdenum dithiocarbamate;
      • (d) molybdenum dithiophosphate;
      • (e) overbased calcium sulfonate;
      • (f) neutral zinc sulfonate; and
      • (g) an antioxidant.
  • The contents of the components in the above composition based on the total mass of the composition preferably are: (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass.
  • Alternatively, the composition of the present invention preferably comprises:
      • (a) a base oil;
      • (b) an aliphatic diurea thickener;
      • (c) molybdenum dithiocarbamate;
      • (d) molybdenum dithiophosphate;
      • (e) overbased calcium sulfonate containing calcium carbonate and having a base number of 300 mgKOH/g or more;
      • (f) neutral zinc sulfonate; and
      • (g) an amine-based antioxidant.
  • The contents of the components in the above composition based on the total mass of the composition preferably are: (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass.
  • Instead, the composition of the present invention preferably comprises:
      • (a) a base oil;
      • (b) an aliphatic diurea thickener in the above formula (1) in which R1 and R3 are both linear alkyl groups having 8 carbon atoms and R2 is diphenylmethane diisocyanate;
      • (c) a mixture of oil-soluble molybdenum dithiocarbamate and oil-insoluble molybdenum dithiocarbamate;
      • (d) molybdenum dithiophosphate;
      • (e) alkyl aromatic calcium sulfonate containing calcium carbonate and having a base number of 300 to 500 mgKOH/g;
      • (f) zinc dinonylnaphthalene sulfonate having a base number of 10 mgKOH/g or less; and
      • (g) alkyl diphenylamine.
  • The contents of the components in the above composition based on the total mass of the composition preferably are: (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass.
  • The grease composition of the present invention is applicable to constant-velocity joints. In particular, it is preferable to apply the grease composition to plunging type constant-velocity joints, especially tripod type constant-velocity joints, and double offset type constant-velocity joints, especially inboard side constant-velocity joints, because the grease composition is excellent in durability and vibration suppression.
  • EXAMPLES [1] Production of Grease Compositions in Examples 1 to 7 and Comparative Examples 1 to 4
  • In a base oil, 1 mol of 4′,4-diphenylmethane diisocyanate and 2 mol of octylamine were reacted, followed by heating and cooling. Thereafter, additives were blended in the ratio specified in Table 1 or 2, and the resultant mixture was kneaded in a three-roll mill to produce a grease composition with a worked penetration of 315. The numerical values in Tables 1 and 2 specify % by mass based on the total mass of the grease composition, unless otherwise specified.
  • [2] Production of Grease Composition in Comparative Example 5
  • A grease composition in Comparative Example 5 was prepared in accordance with the description of Example C4 in Japanese Patent No. 6470851.
  • The components used to prepare the grease compositions are as follows.
  • <Base Oil>
      • Mineral oil (kinematic viscosity at 100° C.: 12.4 mm2/s)
      • Mineral oil+Synthetic oil: poly-α-olefin (kinematic viscosity at 100° C.: 12.0 mm2/s)
    <Additives>
      • MoDTC (oil-insoluble): molybdenum dithiocarbamate (ADEKA SAKURA-LUBE 600, manufactured by Adeka Corporation)
      • MoDTC (oil-insoluble): molybdenum dithiocarbamate (Molyvan A, manufactured by Vanderbilt, used in Comparative Example 5)
      • MoDTC (oil soluble): molybdenum dithiocarbamate (ADEKA SAKURA-LUBE 525, manufactured by Adeka Corporation)
      • MoDTP: Molybdenum dithiophosphate (ADEKA SAKURA-LUBE 300, manufactured by Adeka Corporation)
      • MoDTP: Molybdenum dithiophosphate (Molyvan L, manufactured by Vanderbilt, used in Comparative Example 5)
      • Ca sulfonate (overbased): calcium salt of alkyl aromatic sulfonic acid (LUBRIZOL 5283C, manufactured by The Lubrizol Corporation, base number 375 mgKOH/g)
      • Zn sulfonate (neutral): zinc dinonylnaphthalene sulfonate (NA-SUL ZS, manufactured by KING INDUSTRIES, base number 5 mgKOH/g)
      • Antioxidant
    [2] Evaluation of Durability (1) SRV Test (High Load) [Test Conditions]
      • Test speed: 11.9 mm/s (frequency: 3.3 Hz, stroke: 1.8 mm)
      • Test temperature: 90° C.
      • Load: 5.5 GPa
      • Specimen: Ball (diameter 17.5 mm, SUJ-2)/plate (SUJ-2, surface roughness Rz 0.5 μm)
        [Evaluation criteria]
      • ⊚ (Pass): Friction coefficient of 0.08 or less
      • ◯ (Pass): Friction coefficient of more than 0.08 to 0.10 or less
      • Δ (Pass): Friction coefficient of more than 0.10 to 0.12 or less
      • X (Failure): Occurrence of seizure or friction coefficient of more than 0.12
    (2) SRV Test (Low Load) [Test Conditions]
      • Test speed: 2.0 mm/s (frequency: 3.3 Hz, stroke: 0.3 mm)
      • Test temperature: 95° C.
      • Load: 2.1 GPa
      • Specimen: Ball (diameter 17.5 mm, SUJ-2)/plate (SUJ-2, surface roughness Rz 5 μm)
    [Evaluation Criteria]
      • ◯ (Pass): Friction coefficient of 0.10 or less
      • Δ (Pass): Friction coefficient of more than 0.10 to 0.14 or less
      • X (Failure): Occurrence of seizure or friction coefficient of more than 0.14
    [2] Evaluation of Vibration Suppression (1) TE77 Test
  • A TE77 tester is a vibration friction wear tester under sliding conditions. It has been reported that there is a relationship between vibration caused by a constant-velocity joint as a vibration source and the friction coefficient measured with the TE77 tester under vibration conditions (Japanese Patent Application Publication No. 2010-065194). Therefore, the vibration suppression in a constant-velocity joint was evaluated by using the TE77 tester.
  • [Test Conditions]
      • Test speed: 16 mm/s (frequency: 10 Hz, stroke: 0.8 mm)
      • Test temperature: 40° C.
      • Load: 1.2 GPa
      • Specimen: Ball (17.5 mm diameter, SUJ-2)/Plate (SCM)
    [Evaluation Criteria]
      • ◯ (Pass): Friction coefficient of 0.07 or less
      • Δ (Pass): Friction coefficient of more than 0.07 to 0.10 or less
      • X (Failure): Friction coefficient of more than 0.10
    [Comprehensive Evaluation]
      • ◯ (Pass): The grease composition passed in all of the above test results.
      • X (Failure): The grease composition failed in one or more of the above test results.
  • The results are shown in Tables 1 and 2.
  • TABLE 1
    Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
    (b) Thickener Aliphatic Diurea 6.0 6.0 6.0 6.0 6.0 6.0 6.0
    (a) Base Oil Mineral Oil Balance Balance Balance Balance Balance Balance Balance
    Kinematic Viscosity 12.4 12.4 12.4 12.4 12.4 12.4 12.4
    (mm2/s @100° C.)
    Additives (c) MoDTC Oil-Insoluble 0.8 0.8 0.8 0.8 0.8 0.8
    Oil-Soluble 1.8 1.8 1.8 1.8 1.8 1.8 2.3
    (d) MoDTP 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    (e) Ca Sulfonate Overbased 1.6 3.2 1.1 0.9 1.6 0.2 1.6
    (f) Zn Sulfonate Neutral 1.0 2.8 1.0 0.8 0.6 1.0 1.0
    Antioxidant 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    Comprehensive Evaluation
    Durability SRV Test @High Load
    SRV Test @Low Load Δ Δ
    Vibration TE77 Test Δ Δ Δ Δ
    Suppression
  • TABLE 2
    Comp. Ex. 1 Comp. Ex. 2 Comp. Ex. 3 Comp. Ex. 4 Comp. Ex. 5
    (b) Thickener Aliphatic Diurea 6.0 6.0 6.0 6.0
    Li-OHSt 6.0
    (a) Base Oil Mineral Oil Balance Balance Balance Balance Balance
    Synthetic Oil
    Kinematic Viscosity 12.4 12.4 12.4 12.4 12.0
    (mm2/s @100° C.)
    Additives (c) MoDTC Oil-Insoluble 0.8 0.8 0.8 1.5
    Oil-Soluble 1.8 1.8 1.8
    (d) MoDTP 0.5 0.5 0.5 0.5
    (e) Ca Sulfonate Overbased 1.1 1.6 1.6
    (f) Zn Sulfonate Neutral 1.0 1.0 1.0 3.0
    Antioxidant 0.5 0.5 0.5 0.5 0.3
    Comprehensive Evaluation X X X X X
    Durability SRV Test @High Load X Δ X X X
    SRV Test @Low Load Δ X Δ X
    Vibration TE77 Test Δ X Δ Δ X
    Suppression

Claims (9)

1. A grease composition for constant-velocity joints comprising:
(a) a base oil;
(b) a diurea thickener;
(c) molybdenum dithiocarbamate;
(d) molybdenum dithiophosphate;
(e) overbased calcium sulfonate; and
(f) neutral zinc sulfonate.
2. The grease composition according to claim 1, wherein a content of the component (f) is 0.1 to 10% by mass based on the total mass of the composition.
3. The grease composition according to claim 1, wherein a content of the component (f) is 0.5 to 5% by mass based on the total mass of the composition.
4. The grease composition according to claim 1, wherein a content of the component (f) is 0.8 to 3% by mass based on the total mass of the composition.
5. The grease composition according to claim 1, wherein a content of the component (e) is 0.1 to 10% by mass based on the total mass of the composition.
6. The grease composition according to claim 1, wherein a content of the component (e) is 0.2 to 5% by mass based on the total mass of the composition.
7. The grease composition according to claim 1, wherein a content of the component (e) is 1.2 to 3.5% by mass based on the total mass of the composition.
8. The grease composition according to claim 1, wherein the component (b) is an aliphatic diurea thickener.
9. A constant-velocity joint in which the grease composition according to claim 1 is enclosed.
US18/252,723 2020-11-26 2020-11-26 Grease composition for constant-velocity joints Pending US20230416633A1 (en)

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EP (1) EP4253507A4 (en)
JP (1) JPWO2022113239A1 (en)
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Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6346299A (en) 1986-01-16 1988-02-27 Ntn Toyo Bearing Co Ltd Grease for constant speed joint
JPH0579280A (en) 1991-09-19 1993-03-30 Kajima Corp Tail clearance measuring device for shieled excavating machine
JP4397977B2 (en) 1997-12-10 2010-01-13 協同油脂株式会社 Grease composition for constant velocity joints
JP4102627B2 (en) * 2002-09-13 2008-06-18 株式会社ジェイテクト Rolling bearing
TW200624549A (en) * 2004-11-08 2006-07-16 Thk Co Ltd Grease composition conforming to vibration and guide employing the same
JP5379343B2 (en) * 2006-05-10 2013-12-25 昭和シェル石油株式会社 Grease composition for constant velocity joints
JP5344422B2 (en) * 2008-09-12 2013-11-20 協同油脂株式会社 Grease composition for constant velocity joint and constant velocity joint
JP5113807B2 (en) 2009-06-19 2013-01-09 昭和シェル石油株式会社 Grease composition for constant velocity joints
JP5028701B2 (en) 2009-08-07 2012-09-19 協同油脂株式会社 Grease composition for constant velocity joint and constant velocity joint
US9567548B2 (en) 2012-10-05 2017-02-14 Kyodo Yushi Co., Ltd. Grease composition
JP5641487B2 (en) * 2012-12-21 2014-12-17 協同油脂株式会社 Grease composition
CN107532103B (en) 2015-03-31 2020-03-31 Gkn动力传动系统国际有限责任公司 Grease composition for constant velocity universal joint
JP5807833B1 (en) * 2015-05-16 2015-11-10 有限会社タービュランス・リミテッド Lubricating oil additive and lubricating oil composition
JP6841595B2 (en) * 2015-12-25 2021-03-10 協同油脂株式会社 Lubricant composition for reducer and reducer

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WO2022113239A1 (en) 2022-06-02
CN116601273A (en) 2023-08-15
JPWO2022113239A1 (en) 2022-06-02
EP4253507A4 (en) 2024-04-17
EP4253507A1 (en) 2023-10-04

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