EP0960180A1 - Urea grease composition - Google Patents

Urea grease composition

Info

Publication number
EP0960180A1
EP0960180A1 EP97945872A EP97945872A EP0960180A1 EP 0960180 A1 EP0960180 A1 EP 0960180A1 EP 97945872 A EP97945872 A EP 97945872A EP 97945872 A EP97945872 A EP 97945872A EP 0960180 A1 EP0960180 A1 EP 0960180A1
Authority
EP
European Patent Office
Prior art keywords
urea
grease
urea grease
grease composition
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97945872A
Other languages
German (de)
French (fr)
Other versions
EP0960180B1 (en
Inventor
Ryuichi Masumori
Takahiro Ozaki
Tomoo Munakata
Tsutomu Yoshida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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Publication of EP0960180A1 publication Critical patent/EP0960180A1/en
Application granted granted Critical
Publication of EP0960180B1 publication Critical patent/EP0960180B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
    • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • 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
    • C10M2215/006—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions used as thickening agents
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/026—Amines, e.g. polyalkylene polyamines; Quaternary amines used as thickening agents
    • 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
    • C10M2215/08—Amides
    • C10M2215/0813—Amides used as thickening agents
    • 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
    • C10M2215/1013—Amides of carbonic or haloformic acids used as thickening agents
    • 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
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/12—Partial amides of polycarboxylic acids
    • C10M2215/121—Partial amides of polycarboxylic acids used as thickening agents
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/2206—Heterocyclic nitrogen compounds used as thickening agents
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/227—Phthalocyanines
    • C10M2215/2275—Phthalocyanines used as thickening agents
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044—Polyamides
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • 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
    • 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
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids

Definitions

  • the present invention relates to urea grease compositions and to gears containing such compositions.
  • Petroleum cost has increased sharply since so-called Oil Shock, and resourcing saving and energy saving ideas have been constantly intended in every industrial field, reflecting its influence.
  • CVJ constant velocity joints
  • CVJ is also employed in 4 wheel drive vehicles and vehicles of four wheel independent suspension type, and the demand is growing.
  • CVJ which is also called constant velocity universal joint, is a joint which transmits rotation keeping constant angular speed and torque, and has different types depending on various uses.
  • the lubricating agents used for the CVJ are exposed to severer condition as a motor vehicle achieves higher power and higher speed and CVJ itself becomes compact, and therefore, a grease is demanded which reduces friction and wear on sliding portions.
  • a seal boot member is required to be mounted on CVJ to prevent leaking of a grease and to prevent invasion of foreign materials and water from outside.
  • chloroprene rubber is generally used and polyester resins are also commonly used.
  • a grease which is excellent in low friction and wear resistance suppresses vibration and noise of a vehicle body at a time of starting and accelerating and during driving. Moreover, due to its temperature suppressing effect, durability of a seal boot member can be improved. However, excessive increase of temperature promotes ageing of the seal boot member and degradation of a lubricating agent and extremely shortens the life of CVJ.
  • lithium-based greases have been conveniently used using sulfur-based compounds such as sulfu ⁇ zed fat and oil, sulfurized olefin and the like, lead naphthenate, metal dithiophosphate, metal dithiocarbamate-based additive and the like.
  • sulfur-based compounds such as sulfu ⁇ zed fat and oil, sulfurized olefin and the like, lead naphthenate, metal dithiophosphate, metal dithiocarbamate-based additive and the like.
  • a lithium complex grease and a urea grease which are superior in heat resistance to lithium-based greases have been increasingly used.
  • U.S. Patent No. 4,514,312 discloses a grease using aromatic amine phosphate as an organic additive containing no sulfur in a urea grease.
  • U.S. Patent No. 4,840,740 discloses a grease comprising a urea gresae, an organic molybdenum compound, and zinc dithiophosphate .
  • JP-B Japanese Patent Publication
  • 04-34590(1992) discloses a urea grease comprising as an essential component a sulfur-phosphorus-based extreme pressure additive comprising 1) molybdenum dialkyldithiocarbamate sulfide and 2) one or a combination of two or more selected from the group consisting of sulfurized fat and oil, sulfurized olefin, tricresyl phosphate, trialkyl thiophosphate and zinc dialkyl dithiophosphate.
  • JP-A Japanese Patent Application Laid-Open
  • JP-A No. 08-157859 (1996) discloses the use of as additives a molybdenum dialkyldithiocarbamate sulfide and triphenylphosphoro- thionate
  • JP- A Japanese Patent Application Laid-Open
  • JP- A No. 62-2275197 (1987) discloses the use of as thickening agents a lithium soap of 12-hydroxy fatty acid, lithium phosphate formed from a phosphate such as trimethyl phosphate or triphenyl phosphate.
  • Japanese Patent Application Laid-Open (JP-A) No. 03-231993 (1991) discloses a grease composition using a phosphate oil in a urea compound.
  • the present invention relates to a urea grease which is excellent in frictional properties and wear resistance and also has good fitting property to sealants such as chloroprene rubber and polyester resin. More particularly, the present invention relates to a urea grease composition suitable for application to such parts to be grease-lubricated as constant velocity joints, ball joints, and ball bearings in motor vehicles and bearings and gears of various industrial equipments such as the steel and industrial machines and machine tools .
  • the present invention relates to a urea grease composition
  • a urea grease composition comprising a urea grease and as additives (A) a molybdenum dialkyldithiocarbamate sulfide represented by the formula:
  • R 1 and R 2 each independently represents a group selected from the group consisting of alkyl groups having from 1 to 24 carbon atoms; m is 0 or an integer of from 1 to 3; and n is an integer of from 1 to 4 ; provided that the sum of m and n is 4, and (B) a triphenyl phosphate represented by the formula:
  • the compounds corresponding to the above-mentioned component (A) have a high melting point.
  • examples of those compounds include diethyl sulfide-molybdenum dithiocarbamate, dibutyl-molybdenum dithiocarbamate, diisobutyl sulfide-molybdenum dithiocarbamate, di(2- ethylhexyl) sulfide-molybdenum dithiocarbamate, diamyl sulfide-molybdenum dithiocarbamate, diisoamyl sulfide- molybdenum dithiocarbamate, dilauryl sulfide-molybdenum dithiocarbamate, distearyl sulfide-molybdenum dithiocarbamate.
  • the amount added is from 0.5 to 10% by weight, preferably from 0.5 to 5% by weight based on the total weight.
  • the amount added is less than 0.5% by weight, effect of improvement in friction resistance and wear resistance is generally insufficient, and when over 10% by weight, no further improvement will generally occur.
  • triphenyl phosphate has a melting point of 50 °C and is solid at ambient temperature, it is preferred that the powder is blended with the base grease at a temperature of not less than 50 °C.
  • the amount of component (B) preferably is from 0.1 to 10% by weight, more preferably from 0.1 to 5% by weight based on the total weight. When the amount used is less than 0.1% by weight, improvement in friction resistance and wear resistance properties generally cannot be achieved, and when over 10% by weight, further lubricating ability generally cannot be obtained.
  • the urea compound any of known thickening agents of urea type can be used. For example, diurea, triurea and tetraurea may be used.
  • a mineral oil and/or a synthetic oil can be used as the base oil. If the urea compound is used as a thickening agent it is preferably applied in an amount from 2 to 35% by weight based on the total weight of the base oil and the urea compound.
  • additives such as an antioxidant, anticorrosion agent, extreme pressure agent, polymer and the like can further be added to the composition of the present invention.
  • the urea grease composition according to the invention are especially suitable for use in gears, more specifically constant velocity joints. Therefore, the present invention further relates to gears, more specifically constant velocity joints, containing such grease .
  • Example and Comparative Example The present invention will be specifically described by Examples and Comparative Examples hereinafter, however it is not construed to be limited to them.
  • Additives were added to base greases in blending ratios as shown in Tables 1 to 5 (all of them are shown in % by weight), the mixtures were treated by three-roll mill to obtain greases of Examples and Comparative Examples.
  • the formulations of the base greases are as described below.
  • As the base oil a purified mineral oil having a viscosity of 15 mm z /sec at 100 ° C was used. I . Diurea grease
  • Hydrogenated caster oil fatty acid was dissolved in the base oil, to which was added an aqueous lithium hydroxide solution for neutralization, and the mixture was dehydrated during the reaction. After completion of the dehydration, azelaic acid was added. The reaction was carried out with the help of an aqueous lithium hydroxide solution in the amount necessary for neutralization.
  • the lithium azelate and lithium 12- hydroxystearate soap were mixed and dispersed uniformly to obtain a grease.
  • the amount of lithium 12-hydroxy- stearate as a thickening agent was 7.5% by weight and the amount of lithiumazelate was 2.5% by weight, respectively, based on the total weight of the base oil and the thickening agent.
  • Friction coefficient The following test were conducted regarding friction coefficient, wear resistance and fitting property to a sealant as shown in the tables, and evaluations were made .
  • Friction coefficient after 15 minutes was measured under the following conditions using a Falex testing machine (according to IP/241/69) .
  • Amount of grease about 1 g of grease was applied on a test piece
  • A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVANA A, available from Vanderbilt Co..
  • A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka Kogyo K.K..
  • B is a triphenyl phosphate.
  • A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVANA A, available from Vanderbilt Co..
  • A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka Kogyo K.K..
  • B is a triphenyl phosphate
  • A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVAN A, available from Vanderbilt Co.
  • A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka
  • B is a triphenyl phosphate
  • Vanlube 592 is a trade name of R.T. Vanderbilt Co. Inc., and a viscous liquid (190 SUS/100°C) comprising an aromaticaminephosphate .
  • Lubrizol 1360 is a zinc dialkyldithiophosphate .
  • Lubrizol 5006 is a sulfurized fat and oil.
  • Lubrizol 5340L is a sulfurized olefin.
  • Dailube L-30 is a lead naphthenate of Dainippon Ink and Chemicals, Inc.
  • A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVAN A, available from Vanderbilt Co.
  • A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka
  • B is a triphenyl phosphate
  • Vanlube 592 is a trade name of R.T. Vanderbilt Co. Inc., and a viscous liquid (190 SUS/100°C) comprising an aromaticaminephosphate .
  • Lubrizol 1360 is a zinc dialkyldithiophosphate .
  • Lubrizol 5006 is a sulfurized fat and oil.
  • Lubrizol 5340L is a sulfurized olefin.
  • Dailube L-30 is a lead naphthenate of Dainippon Ink and Chemicals, Inc.
  • Comparative Examples 1 to 7 are all smaller as compared with those of Comparative Examples 1 to 10.
  • Comparative Examples 5, 6, 7, 9 and 10 provide the same degree of good results as the examples according to the invention.
  • these Comparative Examples are inferior in compatability to chloroprene rubber and/or polyester resin .
  • Comparative Example 5 gives a large change in elongation of chloroprene rubber and polyester resin.
  • Comparative Example 6 gives a large change in tensile strength and elongation of chloroprene rubber and polyester resin.
  • Comparative Examples 9 and 10 give relatively large change in elongation of a polyester resin.
  • Examples 1 to 7 give an excellent friction coefficient and wear resistance and also an excellent fitting property to sealants of chloroprene rubber and polyester resins.
  • the grease of the present invention has a low friction coefficient and is excellent in wear resistance. As a result, vibration and noise of CVJ of motor vehicles are suppressed. Further, the grease of the present invention reduces friction in ball joints and wheel bearings of motor vehicles and other various industry machine apparatuses, and can lengthen the life of machine parts.
  • the grease of the present invention is excellent in the fitting property to chloroprene rubber and polyester resin, and delays the degradation of the sealant of a sealed apparatus even at high temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A urea grease composition and gears containing such composition, which composition comprises a urea grease and as additives: (A) a molybdenum dialkyldithiocarbamate sulfide represented by formula (I), wherein R?1 and R2¿ each independently represents a group selected from the group consisting of alkyl groups having from 1 to 24 carbon atoms; m is 0 or an integer of from 1 to 3; and n is an integer of from 1 to 4; provided that the sum of m and n is 4, and (B) a triphenyl phosphate represented by formula (II).

Description

UREA GREASE COMPOSITION
The present invention relates to urea grease compositions and to gears containing such compositions. Petroleum cost has increased sharply since so-called Oil Shock, and resourcing saving and energy saving ideas have been constantly intended in every industrial field, reflecting its influence.
In the motor vehicle industry, compact and light general motor vehicles have been developed, and the number of vehicles employing constant velocity joints (hereinafter, abbreviated as CVJ) have increased.
Further, CVJ is also employed in 4 wheel drive vehicles and vehicles of four wheel independent suspension type, and the demand is growing. CVJ, which is also called constant velocity universal joint, is a joint which transmits rotation keeping constant angular speed and torque, and has different types depending on various uses. The lubricating agents used for the CVJ are exposed to severer condition as a motor vehicle achieves higher power and higher speed and CVJ itself becomes compact, and therefore, a grease is demanded which reduces friction and wear on sliding portions. Further, a seal boot member is required to be mounted on CVJ to prevent leaking of a grease and to prevent invasion of foreign materials and water from outside. As for this material, chloroprene rubber is generally used and polyester resins are also commonly used.
A grease which is excellent in low friction and wear resistance suppresses vibration and noise of a vehicle body at a time of starting and accelerating and during driving. Moreover, due to its temperature suppressing effect, durability of a seal boot member can be improved. However, excessive increase of temperature promotes ageing of the seal boot member and degradation of a lubricating agent and extremely shortens the life of CVJ.
On the other hand, in the steel industry, continuous operation of mechanical equipment has been further developed. With the technical revolution, there have been a strong demand in high quality of a product, improvement in production process capacity, ensuring of reliability of an apparatus, and the like. Lubrication conditions are very severe, since greases used in these mechanical apparatus are in a tough environment, that is, high temperature, contact with water, high possibility of invasion of foreign materials such as scale, and the like, and are continuously exposed to severe conditions day and night. A grease is required which has excellent seal resistance and reduces friction and wear to lengthen the life of mechanical parts and to prevent sudden failure to the utmost. Further, the parts to be lubricated of industrial machinery, machine tools, and the like suffer from considerable friction, and excessive wear causes reduction in accuracy of the machine, so that the mechanical parts have to be replaced. As described above, to reduce friction and save wear is an important object of the present invention .
Therefore, in the parts to be lubricated as described above, lithium-based greases have been conveniently used using sulfur-based compounds such as sulfuπzed fat and oil, sulfurized olefin and the like, lead naphthenate, metal dithiophosphate, metal dithiocarbamate-based additive and the like. Recently, a lithium complex grease and a urea grease which are superior in heat resistance to lithium-based greases have been increasingly used.
Under this situation, as one of typical prior art, U.S. Patent No. 4,514,312 discloses a grease using aromatic amine phosphate as an organic additive containing no sulfur in a urea grease. Further, U.S. Patent No. 4,840,740 discloses a grease comprising a urea gresae, an organic molybdenum compound, and zinc dithiophosphate . Japanese Patent Publication (JP-B) No. 04-34590(1992) discloses a urea grease comprising as an essential component a sulfur-phosphorus-based extreme pressure additive comprising 1) molybdenum dialkyldithiocarbamate sulfide and 2) one or a combination of two or more selected from the group consisting of sulfurized fat and oil, sulfurized olefin, tricresyl phosphate, trialkyl thiophosphate and zinc dialkyl dithiophosphate.
Although some of the greases in the prior art are recognized to have reducing effects in friction and wear, full satisfaction has not been attained. Further, there are disadvantages that sealants deteriorate under high temperature. For example, an aromatic amine phosphate and lead naphthenate degrade polyester resins and a sulfurized fat and oil degrades chloroprene rubber, respectively, and a sulfurized olefin extremely degrades both chloroprene rubber and polyester resins.
Further, in other prior art, Japanese Patent Application Laid-Open (JP-A) No. 08-157859 (1996) discloses the use of as additives a molybdenum dialkyldithiocarbamate sulfide and triphenylphosphoro- thionate, and Japanese Patent Application Laid-Open (JP- A) No. 62-2275197 (1987) discloses the use of as thickening agents a lithium soap of 12-hydroxy fatty acid, lithium phosphate formed from a phosphate such as trimethyl phosphate or triphenyl phosphate. Further, Japanese Patent Application Laid-Open (JP-A) No. 03-231993 (1991) discloses a grease composition using a phosphate oil in a urea compound.
The present invention relates to a urea grease which is excellent in frictional properties and wear resistance and also has good fitting property to sealants such as chloroprene rubber and polyester resin. More particularly, the present invention relates to a urea grease composition suitable for application to such parts to be grease-lubricated as constant velocity joints, ball joints, and ball bearings in motor vehicles and bearings and gears of various industrial equipments such as the steel and industrial machines and machine tools .
The present invention relates to a urea grease composition comprising a urea grease and as additives (A) a molybdenum dialkyldithiocarbamate sulfide represented by the formula:
wherein R1 and R2 each independently represents a group selected from the group consisting of alkyl groups having from 1 to 24 carbon atoms; m is 0 or an integer of from 1 to 3; and n is an integer of from 1 to 4 ; provided that the sum of m and n is 4, and (B) a triphenyl phosphate represented by the formula:
The compounds corresponding to the above-mentioned component (A) have a high melting point. Examples of those compounds include diethyl sulfide-molybdenum dithiocarbamate, dibutyl-molybdenum dithiocarbamate, diisobutyl sulfide-molybdenum dithiocarbamate, di(2- ethylhexyl) sulfide-molybdenum dithiocarbamate, diamyl sulfide-molybdenum dithiocarbamate, diisoamyl sulfide- molybdenum dithiocarbamate, dilauryl sulfide-molybdenum dithiocarbamate, distearyl sulfide-molybdenum dithiocarbamate. They are preferably mixed in the form of powder, and the amount added is from 0.5 to 10% by weight, preferably from 0.5 to 5% by weight based on the total weight. When the amount added is less than 0.5% by weight, effect of improvement in friction resistance and wear resistance is generally insufficient, and when over 10% by weight, no further improvement will generally occur.
As triphenyl phosphate has a melting point of 50 °C and is solid at ambient temperature, it is preferred that the powder is blended with the base grease at a temperature of not less than 50 °C. The amount of component (B) preferably is from 0.1 to 10% by weight, more preferably from 0.1 to 5% by weight based on the total weight. When the amount used is less than 0.1% by weight, improvement in friction resistance and wear resistance properties generally cannot be achieved, and when over 10% by weight, further lubricating ability generally cannot be obtained. As to the urea compound, any of known thickening agents of urea type can be used. For example, diurea, triurea and tetraurea may be used.
As the base oil, a mineral oil and/or a synthetic oil can be used. If the urea compound is used as a thickening agent it is preferably applied in an amount from 2 to 35% by weight based on the total weight of the base oil and the urea compound.
Also, various additives such as an antioxidant, anticorrosion agent, extreme pressure agent, polymer and the like can further be added to the composition of the present invention.
The urea grease composition according to the invention are especially suitable for use in gears, more specifically constant velocity joints. Therefore, the present invention further relates to gears, more specifically constant velocity joints, containing such grease .
Example and Comparative Example The present invention will be specifically described by Examples and Comparative Examples hereinafter, however it is not construed to be limited to them. Additives were added to base greases in blending ratios as shown in Tables 1 to 5 (all of them are shown in % by weight), the mixtures were treated by three-roll mill to obtain greases of Examples and Comparative Examples.
The formulations of the base greases are as described below. As the base oil, a purified mineral oil having a viscosity of 15 mmz/sec at 100°C was used. I . Diurea grease
One mol of diphenylmethane-4 , 4 ' -diisocyanate and 2 mol of octylamine were reacted in the base oil, and the produced urea compound was dispersed uniformly to obtain a grease. The amount of urea compound was 10% by weight based on the total weight of the base oil and the urea compound .
II. Tetraurea grease Two mol of dιphenylmethane-4 , 4 ' -dusocyanate, 2 mol of octylamme, and 1 mol of ethylenediamme were reacted the base oil, and the produced urea compound was dispersed uniformly to obtain a grease. The amount of urea compound was 15% by weight based on the total weight of the base oil and the urea compound.
III. Lithium complex grease
Hydrogenated caster oil fatty acid was dissolved in the base oil, to which was added an aqueous lithium hydroxide solution for neutralization, and the mixture was dehydrated during the reaction. After completion of the dehydration, azelaic acid was added. The reaction was carried out with the help of an aqueous lithium hydroxide solution in the amount necessary for neutralization. The lithium azelate and lithium 12- hydroxystearate soap were mixed and dispersed uniformly to obtain a grease. The amount of lithium 12-hydroxy- stearate as a thickening agent was 7.5% by weight and the amount of lithiumazelate was 2.5% by weight, respectively, based on the total weight of the base oil and the thickening agent.
The following test were conducted regarding friction coefficient, wear resistance and fitting property to a sealant as shown in the tables, and evaluations were made . (1) Friction coefficient
Friction coefficient after 15 minutes was measured under the following conditions using a Falex testing machine (according to IP/241/69) . Rotation speed 290 rpm
Load 890N (200 lb)
Temperature room temperature
Time 15 minutes
Amount of grease about 1 g of grease was applied on a test piece
(2) Wear resistance
According to the four ball type wearing test of
ASTM D2226
Rotation speed 1200 rpm Load 392N (40 kgf)
Temperature 75°C Time 60 minutes
(3) Fitting property to sealant Sealants which were chloroprene rubber of a polyester resin were immersed in respective grease compositions and tested under the following conditions according to the vulcanized rubber physical test of JIS K6301. The tensile strength and elongation before and after the test were measured and change (%) was obtained .
Temperature : 140°C Immersion Time : 96 hrs
Table 1
: A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVANA A, available from Vanderbilt Co..
*2: A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka Kogyo K.K..
*3*: B is a triphenyl phosphate.
Table 2
A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVANA A, available from Vanderbilt Co..
A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka Kogyo K.K..
B is a triphenyl phosphate.
Table 3
D
A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVAN A, available from Vanderbilt Co.
A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka
Kogyo K.K..
B is a triphenyl phosphate.
Vanlube 592 is a trade name of R.T. Vanderbilt Co. Inc., and a viscous liquid (190 SUS/100°C) comprising an aromaticaminephosphate .
Lubrizol 1360 is a zinc dialkyldithiophosphate .
* 6 Lubrizol 5006 is a sulfurized fat and oil.
Lubrizol 5340L is a sulfurized olefin.
Dailube L-30 is a lead naphthenate of Dainippon Ink and Chemicals, Inc.
Table 4
A-l is a molybdenum dialkyldithiocarbamate sulfide, MOLYVAN A, available from Vanderbilt Co.
A-2 is a molybdenum dialkyldithiocarbamate sulfide, SAKURALUBE 600, available from Asahi Denka
Kogyo K.K..
B is a triphenyl phosphate.
Vanlube 592 is a trade name of R.T. Vanderbilt Co. Inc., and a viscous liquid (190 SUS/100°C) comprising an aromaticaminephosphate .
Lubrizol 1360 is a zinc dialkyldithiophosphate .
Lubrizol 5006 is a sulfurized fat and oil.
Lubrizol 5340L is a sulfurized olefin.
Dailube L-30 is a lead naphthenate of Dainippon Ink and Chemicals, Inc.
Table 5
Table 6
The friction coefficients in Examples 1 to 7 are all smaller as compared with those of Comparative Examples 1 to 10. Regarding wear resistance, Comparative Examples 5, 6, 7, 9 and 10 provide the same degree of good results as the examples according to the invention. However, these Comparative Examples are inferior in compatability to chloroprene rubber and/or polyester resin .
For example, Comparative Example 5 gives a large change in elongation of chloroprene rubber and polyester resin. Comparative Example 6 gives a large change in tensile strength and elongation of chloroprene rubber and polyester resin. Comparative Examples 9 and 10 give relatively large change in elongation of a polyester resin. Examples 1 to 7 give an excellent friction coefficient and wear resistance and also an excellent fitting property to sealants of chloroprene rubber and polyester resins.
The grease of the present invention has a low friction coefficient and is excellent in wear resistance. As a result, vibration and noise of CVJ of motor vehicles are suppressed. Further, the grease of the present invention reduces friction in ball joints and wheel bearings of motor vehicles and other various industry machine apparatuses, and can lengthen the life of machine parts.
The grease of the present invention is excellent in the fitting property to chloroprene rubber and polyester resin, and delays the degradation of the sealant of a sealed apparatus even at high temperature.

Claims

C L A I M S
1. A urea grease composition comprising a urea grease and as additives (A) a molybdenum dialkyldithiocarbamate sulfide represented by the formula:
wherein R1 and R2 each independently represents a group selected from the group consisting of alkyl groups having from 1 to 24 carbon atoms; m is 0 or an integer of from 1 to 3; and n is an integer of from 1 to 4 ; τ ϊri i-jpri +h,-t the sum of m and n is 4, and (B) a triphenyl phosphate represented by the formula:
2. The urea grease composition according to claim 1, wherein said component (A) and said component (B) are blended in an amount of from 0.5 to 10% by weight and from 0.1 to 10% by weight, respectively, based on the total weight of the urea grease composition.
3. The urea grease composition according to claim 1 or 2, wherein said urea grease is composed of a base oil and as a thickening agent a urea compound, the proportion of the urea compound being from 2 to 35% by weight based on the total weight of the base oil and the urea compound.
. Gears containing a urea grease composition according to anyone of claims 1-3.
5. Gears according to claim 4, which gears are constant velocity joints.
26
EP97945872A 1996-10-18 1997-10-17 Urea grease composition Expired - Lifetime EP0960180B1 (en)

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PCT/EP1997/005914 WO1998017748A1 (en) 1996-10-18 1997-10-17 Urea grease composition

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US6376432B1 (en) * 2001-03-26 2002-04-23 Exxonmobil Research And Engineering Company Low friction grease for constant velocity universal joints, particularly plunging type joints that is compatible with silicone elastomer boots
JP2004059604A (en) * 2002-07-24 2004-02-26 Nippon Oil Corp Grease composition
JPWO2004018594A1 (en) * 2002-08-21 2005-12-08 シチズン時計株式会社 Grease composition for precision equipment and watch using the same
JP2005008744A (en) 2003-06-18 2005-01-13 Showa Shell Sekiyu Kk Grease composition
JP2005248034A (en) 2004-03-04 2005-09-15 Ntn Corp Grease composition, its preparation method, and antifriction bearing filled with the grease composition
JP4776193B2 (en) * 2004-09-07 2011-09-21 Ｎｔｎ株式会社 Grease composition for automobile wheel bearing
JP4809603B2 (en) 2004-11-25 2011-11-09 本田技研工業株式会社 Constant velocity joint
JP4461000B2 (en) * 2004-11-25 2010-05-12 本田技研工業株式会社 Grease composition for constant velocity joint and constant velocity joint
JP5335019B2 (en) * 2011-03-07 2013-11-06 Ｎｔｎ株式会社 Grease composition for automobile wheel bearing
JP5826626B2 (en) 2011-12-22 2015-12-02 昭和シェル石油株式会社 Grease composition
JP6292569B2 (en) * 2013-12-04 2018-03-14 協同油脂株式会社 Grease composition for constant velocity joint and constant velocity joint enclosing the grease composition
CN104164286A (en) * 2014-08-05 2014-11-26 中国石油化工股份有限公司 Lubricating grease composition for steering ball joint and preparation method of lubricating grease composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62207397A (en) * 1986-03-06 1987-09-11 Kyodo Yushi Kk Extreme-pressure grease composition
US5133888A (en) * 1990-09-28 1992-07-28 Amoco Corporation Cruise missile engine bearing grease
JP3001171B2 (en) * 1993-05-25 2000-01-24 昭和シェル石油株式会社 Urea grease composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9817748A1 *

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CA2268286A1 (en) 1998-04-30
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KR20000049192A (en) 2000-07-25

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