EP2066770A2 - Lubricating grease composition - Google Patents

Lubricating grease composition

Info

Publication number
EP2066770A2
EP2066770A2 EP07803331A EP07803331A EP2066770A2 EP 2066770 A2 EP2066770 A2 EP 2066770A2 EP 07803331 A EP07803331 A EP 07803331A EP 07803331 A EP07803331 A EP 07803331A EP 2066770 A2 EP2066770 A2 EP 2066770A2
Authority
EP
European Patent Office
Prior art keywords
lubricating grease
weight
grease composition
extreme
benzothiazolylsulphenamide
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.)
Withdrawn
Application number
EP07803331A
Other languages
German (de)
French (fr)
Inventor
Koichi Numazawa
Takahiro Ozaki
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP2066770A2 publication Critical patent/EP2066770A2/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix 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
    • C10M2207/128—Carboxylix 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
    • C10M2207/1285—Carboxylix 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • This invention provides a lubricating grease composition, and in particular a lubricating grease composition to be used at lubrication points where extreme-pressure properties and seal-resistance properties at high loads are required, such as in the bearings, gears, suspensions, joints and steering gear of domestic electrical appliances, construction machinery, transportation machinery, agricultural machinery, steel- making plant and machinery, and so on.
  • extreme-pressure greases containing molybdenum disulphide, sulphur-type, phosphorus-type or sulphur/phosphorus-type additives, or organomolybdenum compounds have been employed for greases to be used, for example, in coupling components or ball joints of suspensions and steering gear where oscillating and rotating motions or reciprocating motion occur.
  • extreme-pressure greases include urea greases containing as their essential constituents sulphurised molybdenum dialkyl dithiocarbamates and sulphur/phosphorus-type extreme- pressure additives comprised of one or a blend of two or more selected from a group comprised of sulphurised oils and fats, sulphurised olefins, tricresyl phosphate, trialkyl dithiophosphates or zinc dialkyl dithiophosphates . See for example Japanese Patent 4-34590.
  • a sealing material such as a boot or a dust cover is used in order to create a tight seal so that the grease is reliably supplied to the lubrication points and to prevent ingress of muddy water or dust from outside.
  • chloroprene rubbers, nitrile rubbers, silicone rubbers, polyester-type elastomers, polyolefin-type rubbers and so on are used, but chloroprene rubbers, which have excellent mechanical strength, flexibility, heat resistance and oil resistance and which are low in cost, are used in particular.
  • molybdenum dialkyl dithiocarbamates are thermally stable and compatibility with seals is relatively good, but additives such as the aforementioned sulphurised oils and fats, sulphurised olefins and zinc dialkyl (aryl) dithiophosphates which are used therewith in order to enhance further the lubricating performance of the molybdenum dialkyl dithiocarbamates have a tendency to be detrimental to the seal-resistance properties .
  • this invention is intended to provide excellent grease compositions which have high extreme- pressure properties and which also do not damage sealing material and are superior in regard to compatibility therewith.
  • the present invention provides a lubricating grease composition
  • a lubricating grease composition comprising a base oil, the composition further comprising: (A) from 0.1 to 3% by weight of a molybdenum dialkyl dithiocarbamate,- (B) from 0.1 to 3% by weight of one or more benzothiazole compounds; and (C) from 0.1 to 3% by weight of one or more calcium sulphonates .
  • this invention provides a lubricating grease composition wherein from 0.1 to 3% by weight of a molybdenum dialkyl dithiocarbamate as shown in the undermentioned Formula 1 [Formula 1]
  • Rl denotes an alkyl group having from 1 to 10 carbons or an alkylmercapto group
  • molybdenum dialkyl dithiocarbamates used in this invention are known to improve extreme-pressure properties and wear-resistance in greases, but recent years have seen PRTR controlled substances (PRTR Law,- Pollutant Release Transfer Register) and a desire to use molybdenum compounds as little as possible, or to use replacement compounds for molybdenum compounds, in view of concerns about the environment and so on.
  • PRTR controlled substances PRTR Law,- Pollutant Release Transfer Register
  • This invention reduces to the utmost the amount of molybdenum dialkyl dithiocarbamates used and, by incorporating with these the aforementioned benzothiazole compounds and calcium sulphonates, is not only capable of improving the extreme-pressure properties but is also capable of improving compatibility between the chloroprene rubber in sealing materials and the grease .
  • thickening agent optionally but preferably incorporated in the aforementioned base oil it is possible to use lithium soaps, lithium complex soaps and diurea, triurea, tetraurea, polyurea and other urea compounds .
  • alkyl groups having from 1 to 24 carbons are preferably used for the alkyl groups, but alkyl groups having from 3 to 18 carbons are preferred.
  • molybdenum dialkyl dithiocarbamates mention be made of sulphurised molybdenum diethyl dithiocarbamate, sulphurised molybdenum dipropyl dithiocarbamate, sulphurised molybdenum dibutyl dithiocarbamate, sulphurised molybdenum dipentyl dithiocarbamate, sulphurised molybdenum dihexyl dithiocarbamate, sulphurised molybdenum dioctyl dithiocarbamate, sulphurised molybdenum didecyl dithiocarbamate, sulphurised molybdenum didodecyl dithiocarbamate, sulphurised molybdenum (butylphenyl) dithiocarbamate, sulphurised molybdenum (nonylphenyl) dithiocarbamate, sulphurised oxy
  • benzothiazole compounds 2- mercaptobenzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide, N-cyclohexyl-2- benzothiazolylsulphenamide , N-oxydiethylene-2 - benzothiazolylsulphenamide and 2- (4- morpholinyldithio) benzothiazole exist, for example, and these may be used singly or in mixtures.
  • 2-mercaptobenzothiazole has previously been proposed as a constituent in metalworking fluids and as a constituent in cutting and grinding process fluids
  • 2- (4 -morpholinyldithio) benzothiazole has been disclosed as a constituent in aqueous lubricants for use in plastic working of metals.
  • the aforementioned calcium sulphonates used in this invention may be ordinary calcium sulphonates, and as examples mention may be made of calcium salts of petroleum sulphonic acid, calcium salts of alkyl aromatic sulphonic acids, overbased calcium salts of petroleum sulphonic acid and overbased calcium salts of alkyl aromatic sulphonic acids. Further, these may be used singly or in suitable mixtures .
  • the amount of the aforementioned molybdenum dialkyl dithiocarbamates to be incorporated in the grease is from 0.1 to 3% by weight, and in respect of the aforementioned 2-mercaptobenzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide, N-cyclohexyl-2- benzothiazolylsulphenamide, N-oxydiethylene-2- benzothiazolylsulphenamide or 2- (4 -morpholinyldithio) benzothiazole, at least one is preferably incorporated in the order of from 0.1 to 3% by weight and calcium sulphonates in the order of from 0.1 to 3% by weight.
  • the amount to be incorporated is preferably of the order of from 0.5 to 1% by weight.
  • lubricating grease composition of this invention it is appropriate to incorporate of the order of from 0.5 to 1% by weight . It is possible in the lubricating grease composition of this invention to use also, as appropriate, in addition to the aforementioned blend constituents, additives such as anti-oxidants, rust preventatives, extreme-pressure additives and anti-wear agents.
  • This invention reduces to the utmost the amount used of molybdenum dialkyl dithiocarbamates, which are PRTR controlled substances, and, by incorporating with these the aforementioned benzothiazole compounds, such as 2-mercapto benzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide , N-cyclohexyl - 2 - benzothiazolylsulphenamide, N-oxydiethylene- 2- benzothiazolylsulphenamide and 2- (4-morpholinyldithio) benzothiazole, and the aforementioned calcium sulphonates, not only is it capable of improving the extreme-pressure properties but it also improves compatibility between the chloroprene rubber in sealing materials and the grease.
  • benzothiazole compounds such as 2-mercapto benzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide , N-cyclohexyl - 2 - benzothiazo
  • Diphenylmethane-4,4 ' -diisocyante (295.2 g) and octylamine (304.8 g) were reacted in a refined mineral oil with a kinetic viscosity of approximately 15 mm 2 /s at 100 0 C (5400 g) , until the diurea compound produced was uniformly dispersed and a grease obtained.
  • the amount of the urea compound included was 10% by weight.
  • This urea based grease had a penetration of 283 and dropping point of 263°C as defined in JIS-K2220 (25 0 C, 60W) .
  • Lithium-12-hydroxystearate (630 g) was dissolved in a refined mineral oil with a kinetic viscosity of approximately 15 mm 2 /s at 100 0 C (6370 g) , until it was uniformly dispersed and a grease obtained.
  • the amount of the lithium soap included was 9% by weight.
  • This lithium soap based grease had a penetration of 268 and dropping point of 198 0 C as defined in JIS-K2220 (25°C, 60W) .
  • Molybdenum dialkyl dithiocarbamate (MoDTC) : The commercial product called “Molyvan A” of Vanderbilt Ltd. was used.
  • Calcium sulphonate Calcium salt of petroleum sulphonic acid
  • Zinc dialkyl dithiocarbamate (ZnDTC): The commercial product called “Lubrizol 1395" of Lubrizol Ltd. was used.
  • Test method Four-ball tests were carried out in accordance with ASTM D2596. Test conditions: * Speed 1770+60 rpm
  • Test method A chloroprene rubber immersion test was carried out in accordance with JIS K6258. Test conditions: (1) Immersion for 120 hours at 14O 0 C was carried out in respect of the lubricating grease compositions using a urea based grease.
  • Comparative Examples 2, 3, 4, 5, 8 and 10 all exhibited a large value for weld load at 3089 N and so extreme-pressure properties were high, but elongation change was from -36.6% to -62.4% and tensile strength change from -37.2% to -64.3%, in all cases above -25%, so that compatibility with sealing material was evidently poor. Also, in the cases of Comparative Examples 1 and 7 with base greases alone, as mentioned above there was small elongation change and tensile change strength of the rubber, so that compatibility with sealing material was good, but extreme-pressure properties were low. In the case, too, of an example of the prior art as shown in Comparative Example 2, the extreme-pressure properties were high but elongation change and tensile strength change were large, so that compatibility with sealing material was inferior. Furthermore, from a comparison of Example 1 and

Abstract

The present invention aims to improve the extreme-pressure properties and compatibility with seals of lubricating grease compositions used at lubrication points where extreme-pressure properties and seal- resistance properties at high loads are required in various kinds of machinery. To this end the present invention provides a lubricating grease composition wherein from 0.1 to 3% by weight of a molybdenum dialkyl dithiocarbamate, from 0.1 to 3% by weight of benzothiazole compounds and from 0.1 to 3% by weight of calcium sulphonates are incorporated in a grease in which a thickening agent is blended in the base oil.

Description

LUBRICATING GREASE COMPOSITION
This invention provides a lubricating grease composition, and in particular a lubricating grease composition to be used at lubrication points where extreme-pressure properties and seal-resistance properties at high loads are required, such as in the bearings, gears, suspensions, joints and steering gear of domestic electrical appliances, construction machinery, transportation machinery, agricultural machinery, steel- making plant and machinery, and so on. Hitherto, extreme-pressure greases containing molybdenum disulphide, sulphur-type, phosphorus-type or sulphur/phosphorus-type additives, or organomolybdenum compounds have been employed for greases to be used, for example, in coupling components or ball joints of suspensions and steering gear where oscillating and rotating motions or reciprocating motion occur.
Known examples of such extreme-pressure greases include urea greases containing as their essential constituents sulphurised molybdenum dialkyl dithiocarbamates and sulphur/phosphorus-type extreme- pressure additives comprised of one or a blend of two or more selected from a group comprised of sulphurised oils and fats, sulphurised olefins, tricresyl phosphate, trialkyl dithiophosphates or zinc dialkyl dithiophosphates . See for example Japanese Patent 4-34590.
When greases are used in the aforementioned applications, a sealing material such as a boot or a dust cover is used in order to create a tight seal so that the grease is reliably supplied to the lubrication points and to prevent ingress of muddy water or dust from outside. For this sealing material, chloroprene rubbers, nitrile rubbers, silicone rubbers, polyester-type elastomers, polyolefin-type rubbers and so on are used, but chloroprene rubbers, which have excellent mechanical strength, flexibility, heat resistance and oil resistance and which are low in cost, are used in particular.
However, under the more severe lubricating conditions the values for properties such as elongation and tensile strength are considerably downgraded because of swelling or contraction of the sealing material under effects due to heat, and it no longer performs its function as a seal .
For this reason, not only are the greases required to have a long life and a lubricating action which is capable of improving the extreme-pressure properties and load-bearing characteristics in respect of the lubrication points, an important factor also is that they have excellent compatibility with the sealing material by not damaging the sealing material which is in contact with the grease.
Among the various types of additives added to greases, molybdenum dialkyl dithiocarbamates are thermally stable and compatibility with seals is relatively good, but additives such as the aforementioned sulphurised oils and fats, sulphurised olefins and zinc dialkyl (aryl) dithiophosphates which are used therewith in order to enhance further the lubricating performance of the molybdenum dialkyl dithiocarbamates have a tendency to be detrimental to the seal-resistance properties .
Therefore, this invention is intended to provide excellent grease compositions which have high extreme- pressure properties and which also do not damage sealing material and are superior in regard to compatibility therewith.
By dint of repeated investigations and experiments to improve further the extreme-pressure properties of greases and also to obtain greases with superior compatibility with the chloroprene rubbers that are widely used as sealing material, the inventors have found that blends of specific additives which have a significant effect as regards the aforementioned extreme- pressure properties and compatibility with seals can be obtained.
The present invention provides a lubricating grease composition comprising a base oil, the composition further comprising: (A) from 0.1 to 3% by weight of a molybdenum dialkyl dithiocarbamate,- (B) from 0.1 to 3% by weight of one or more benzothiazole compounds; and (C) from 0.1 to 3% by weight of one or more calcium sulphonates . In particular this invention provides a lubricating grease composition wherein from 0.1 to 3% by weight of a molybdenum dialkyl dithiocarbamate as shown in the undermentioned Formula 1 [Formula 1]
(where R denotes an alkyl group of from 1 to 24 carbons) , from 0.1 to 3% by weight, as a benzothiazole compound, of at least one of 2-mercapto-benzothiazole or a 2-mercapto- benzothiazole derivative as shown in the undermentioned Formula 2 [Formula 2] - A -
(H)
(where Rl denotes an alkyl group having from 1 to 10 carbons or an alkylmercapto group) or N-tert-butyl-2- benzothiazolylsulphenamide, N- cyclohexyl-2- benzothiazolylsulphenamide, N- oxydiethylene-2- benzothiazolylsulphenamide or 2- (4- morpholinyldithio) benzothiazole and from 0.1 to 3% by weight of calcium sulphonates are incorporated in a grease in which a thickening agent is blended in the base oil. The aforementioned molybdenum dialkyl dithiocarbamates used in this invention are known to improve extreme-pressure properties and wear-resistance in greases, but recent years have seen PRTR controlled substances (PRTR Law,- Pollutant Release Transfer Register) and a desire to use molybdenum compounds as little as possible, or to use replacement compounds for molybdenum compounds, in view of concerns about the environment and so on.
This invention, as mentioned above, reduces to the utmost the amount of molybdenum dialkyl dithiocarbamates used and, by incorporating with these the aforementioned benzothiazole compounds and calcium sulphonates, is not only capable of improving the extreme-pressure properties but is also capable of improving compatibility between the chloroprene rubber in sealing materials and the grease .
For the base oil of the greases of this invention it is possible to use mineral oils, vegetable oils and synthetic oils such as ester oils, ether oils and hydrocarbon oils, or mixtures thereof.
For the thickening agent optionally but preferably incorporated in the aforementioned base oil it is possible to use lithium soaps, lithium complex soaps and diurea, triurea, tetraurea, polyurea and other urea compounds .
In the aforementioned molybdenum dialkyl dithiocarbamates used in this invention, alkyl groups having from 1 to 24 carbons are preferably used for the alkyl groups, but alkyl groups having from 3 to 18 carbons are preferred.
As specific examples of such molybdenum dialkyl dithiocarbamates mention be made of sulphurised molybdenum diethyl dithiocarbamate, sulphurised molybdenum dipropyl dithiocarbamate, sulphurised molybdenum dibutyl dithiocarbamate, sulphurised molybdenum dipentyl dithiocarbamate, sulphurised molybdenum dihexyl dithiocarbamate, sulphurised molybdenum dioctyl dithiocarbamate, sulphurised molybdenum didecyl dithiocarbamate, sulphurised molybdenum didodecyl dithiocarbamate, sulphurised molybdenum (butylphenyl) dithiocarbamate, sulphurised molybdenum (nonylphenyl) dithiocarbamate, sulphurised oxymolybdenum diethyl dithiocarbamate, sulphurised oxymolybdenum dipropyl dithiocarbamate, sulphurised oxymolybdenum dibutyl dithiocarbamate, sulphurised oxymolybdenum dipentyl dithiocarbamate, sulphurised oxymolybdenum dihexyl dithiocarbamate, sulphurised oxymolybdenum dioctyl dithiocarbamate, sulphurised oxymolybdenum didecyl dithiocarbamate, sulphurised oxymolybdenum didodecyl dithiocarbamate, sulphurised oxymolybdenum (butylphenyl) dithiocarbamate, sulphurised oxymolybdenum (nonylphenyl) dithiocarbamate and mixtures thereof .
For the aforementioned benzothiazole compounds, 2- mercaptobenzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide, N-cyclohexyl-2- benzothiazolylsulphenamide , N-oxydiethylene-2 - benzothiazolylsulphenamide and 2- (4- morpholinyldithio) benzothiazole exist, for example, and these may be used singly or in mixtures. The aforementioned 2-mercaptobenzothiazole has previously been proposed as a constituent in metalworking fluids and as a constituent in cutting and grinding process fluids, and 2- (4 -morpholinyldithio) benzothiazole has been disclosed as a constituent in aqueous lubricants for use in plastic working of metals.
The aforementioned calcium sulphonates used in this invention may be ordinary calcium sulphonates, and as examples mention may be made of calcium salts of petroleum sulphonic acid, calcium salts of alkyl aromatic sulphonic acids, overbased calcium salts of petroleum sulphonic acid and overbased calcium salts of alkyl aromatic sulphonic acids. Further, these may be used singly or in suitable mixtures .
The amount of the aforementioned molybdenum dialkyl dithiocarbamates to be incorporated in the grease is from 0.1 to 3% by weight, and in respect of the aforementioned 2-mercaptobenzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide, N-cyclohexyl-2- benzothiazolylsulphenamide, N-oxydiethylene-2- benzothiazolylsulphenamide or 2- (4 -morpholinyldithio) benzothiazole, at least one is preferably incorporated in the order of from 0.1 to 3% by weight and calcium sulphonates in the order of from 0.1 to 3% by weight. If more than 3% by weight of the aforementioned molybdenum dialkyl dithiocarbamates is incorporated, there may either be no change in effect or the effect may even reverse. The amount to be incorporated is preferably of the order of from 0.5 to 1% by weight.
Also in the case of the aforementioned 2-mercapto benzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide, N-cyclohexyl-2- benzothiazolylsulphenamide , N-oxydiethylene-2 - benzothiazolylsulphenamide or 2- (4-morpholinyldithio) benzothiazole, if the amount included in the grease is greater than 3% by weight the effect is either the same or even the reverse. Normally, it is preferable to use of the order of from 0.5 to 1% by weight. For the aforementioned calcium sulphonates, too, the effect is the same, or the reverse, if more than the aforementioned 3% by weight is used. For preference it is appropriate to incorporate of the order of from 0.5 to 1% by weight . It is possible in the lubricating grease composition of this invention to use also, as appropriate, in addition to the aforementioned blend constituents, additives such as anti-oxidants, rust preventatives, extreme-pressure additives and anti-wear agents. This invention, as mentioned above, reduces to the utmost the amount used of molybdenum dialkyl dithiocarbamates, which are PRTR controlled substances, and, by incorporating with these the aforementioned benzothiazole compounds, such as 2-mercapto benzothiazole, N-tert-butyl-2- benzothiazolylsulphenamide , N-cyclohexyl - 2 - benzothiazolylsulphenamide, N-oxydiethylene- 2- benzothiazolylsulphenamide and 2- (4-morpholinyldithio) benzothiazole, and the aforementioned calcium sulphonates, not only is it capable of improving the extreme-pressure properties but it also improves compatibility between the chloroprene rubber in sealing materials and the grease.
Further, physical changes in sealing material in contact with grease are considered to be due chiefly to two factors . One is that the base oil of the grease and additives penetrate the sealing material and give rise to swelling, thus softening the material. The other is that plasticisers in the sealing material leach into the grease, causing compression and hardening. It is believed that these actions occur when affinity between the thickening agent and base oil and the additives collapses, but in the present lubricating grease compositions which include the aforementioned additives in a good balance it can be conjectured that this will perform the function of inhibiting the swelling and contraction of the sealing material. Examples
The invention is explained below by means of examples of embodiment, but the invention is not in any way limited to these.
The lubricating grease compositions of Examples 1 to 5 and Comparative Examples 1 to 11 used to contrast therewith were obtained by proportionately incorporating the base groups and additives shown below and, after adding the various additives to the base greases, by kneading with a three-roll mill and finishing to a uniform consistency. 1. Base greases (1) Urea grease - S -
Diphenylmethane-4,4 ' -diisocyante (295.2 g) and octylamine (304.8 g) were reacted in a refined mineral oil with a kinetic viscosity of approximately 15 mm2/s at 1000C (5400 g) , until the diurea compound produced was uniformly dispersed and a grease obtained. The amount of the urea compound included was 10% by weight. This urea based grease had a penetration of 283 and dropping point of 263°C as defined in JIS-K2220 (250C, 60W) .
(2) Lithium soap grease
Lithium-12-hydroxystearate (630 g) was dissolved in a refined mineral oil with a kinetic viscosity of approximately 15 mm2/s at 1000C (6370 g) , until it was uniformly dispersed and a grease obtained. The amount of the lithium soap included was 9% by weight. This lithium soap based grease had a penetration of 268 and dropping point of 1980C as defined in JIS-K2220 (25°C, 60W) .
2. Molybdenum dialkyl dithiocarbamate (MoDTC) : The commercial product called "Molyvan A" of Vanderbilt Ltd. was used.
3. 2-mercaptobenzothiazole
4. 2- (4-morpholinyldithio) benzothiazole
5. Calcium sulphonate : Calcium salt of petroleum sulphonic acid
6. Zinc dialkyl dithiocarbamate (ZnDTC): The commercial product called "Lubrizol 1395" of Lubrizol Ltd. was used.
7. Sulphurised olefin: The commercial product called "Anglamol 33" of Lubrizol Ltd. was used. 8. Calcium salicylate: The commercial product called
"M7121" of Infineum Ltd. was used.
The following tests were carried out in respect of the extreme-pressure properties and seal compatibility of the lubricating grease compositions of Examples 1 to 5 and Comparative Examples 1 to 11 shown in Tables 1 to 3 , and evaluations were made.
Extreme-pressure tests
Test method: Four-ball tests were carried out in accordance with ASTM D2596. Test conditions: * Speed 1770+60 rpm
* Duration 10 seconds
* Temperature Room temperature Test objective: The weld load (N) was obtained. Seal compatibility tests
Test method: A chloroprene rubber immersion test was carried out in accordance with JIS K6258. Test conditions: (1) Immersion for 120 hours at 14O0C was carried out in respect of the lubricating grease compositions using a urea based grease.
(2) Immersion for 120 hours at 12O0C was carried out in respect of the lubricating grease compositions using a lithium soap. Test objective: Elongation change (%) and change in tensile strength (%) were obtained. (JIS K6251) Evaluation criteria: If both elongation change (%) and change in tensile strength (%) were within 25% (0 ~ - 25%) , an evaluation as satisfactory could be given. Results of tests
The test results for the examples and comparative examples are shown in Tables 1 to 3. Evaluation; discussion
As shown by the results in Table 1, all the Examples 1 to 5 show large values of 3089 N for weld load under extreme-pressure properties, so that it can be seen that the extreme-pressure properties are high. Also, with an elongation change of from -13.8% to -24.9% and a tensile strength change of from -18.5% to -24.2%, all cases are under -25%, so that it can be seen that they have good compatibility with sealing material.
In contrast, as shown by the results in Tables 2 and 3, in the case of Comparative Examples 1, 6, 7 and 11, elongation change was from -12.2% to -16.5% and tensile strength change from -13.8% to -18.6%, in all cases under -25% and so having good compatibility with sealing material, but the weld load was from 1236 N to 1570 N and so extreme-pressure properties were low, so that evidently these would not be suitable as lubricating grease compositions. Also, Comparative Example 9 exhibited a low weld load value of 1961 N and so extreme- pressure properties were low, while elongation change was -35.1% and tensile strength change -37.2%, both under - 25%, so that compatibility with sealing material was poor.
Comparative Examples 2, 3, 4, 5, 8 and 10 all exhibited a large value for weld load at 3089 N and so extreme-pressure properties were high, but elongation change was from -36.6% to -62.4% and tensile strength change from -37.2% to -64.3%, in all cases above -25%, so that compatibility with sealing material was evidently poor. Also, in the cases of Comparative Examples 1 and 7 with base greases alone, as mentioned above there was small elongation change and tensile change strength of the rubber, so that compatibility with sealing material was good, but extreme-pressure properties were low. In the case, too, of an example of the prior art as shown in Comparative Example 2, the extreme-pressure properties were high but elongation change and tensile strength change were large, so that compatibility with sealing material was inferior. Furthermore, from a comparison of Example 1 and
Comparative Example 3, it can be seen that the effect of improving seal compatibility is small with dispersants other than the calcium sulphonates of this invention. Table 1
Table 2
Table 3

Claims

C L A I M S
1. A lubricating grease composition comprising a base oil, the composition further comprising: (A) from 0.1 to 3% by weight of a molybdenum dialkyl dithiocarbamate; (B) from 0.1 to 3% by weight of one or more benzothiazole compounds; and (C) from 0.1 to 3% by weight of one or more calcium sulphonates .
2. A lubricating grease composition according to Claim 1 wherein the molybdenum dialkyl dithiocarbamate has the Formula 1 below, [Formula 1]
wherein R is an alkyl group having from 1 to 24 carbon atoms .
3. A lubricating grease composition according to Claim 1 or Claim 2 wherein the one or more benzothiazole compounds include at least one of 2- mercaptobenzothiazole, or a derivative thereof having the Formula 2 , [Formula 2]
(H) wherein Rl denotes an alkyl group having from 1 to 10 carbons or an alkyl mercapto group .
4. A lubricating grease composition according to any one of Claims 1 to 3 , wherein the one or more benzothiazole compounds include N-tert-butyl-2- benzothiazolylsulphenamide, N-cyclohexyl-2- benzothiazolylsulphenamide, N-oxydiethylene-2- benzothiazolylsulphenamide or 2- (4- morpholinyldithio) benzothiazole .
5. A lubricating grease composition according to any one of Claims 1 to 4 , further comprising a thickening agent.
6. Use of the lubricating grease composition according to any one of Claims 1 to 5 at lubrication points where extreme-pressure properties and seal-resistance properties at high loads are required.
7. Method for improving the lubrication at lubrication points where extreme-pressure properties and seal- resistance properties at high loads are required, by using the lubricating grease composition according to any one of Claims 1 to 5.
EP07803331A 2006-09-08 2007-09-07 Lubricating grease composition Withdrawn EP2066770A2 (en)

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JP5214649B2 (en) * 2010-02-26 2013-06-19 協同油脂株式会社 Grease composition for hub unit bearing using angular ball bearing and hub unit bearing
CN105296052A (en) * 2015-11-20 2016-02-03 沈阳黎明航空发动机(集团)有限责任公司 Nitrile rubber-resistant low-temperature lubricating grease
CN106350187A (en) * 2016-08-29 2017-01-25 江苏博格东进管道设备有限公司 Preparation method of liquid composition for processing lubrication of pipelines
CN108949296B (en) * 2018-08-15 2021-11-05 江苏四新界面剂科技有限公司 Monocrystalline silicon cutting surfactant

Family Cites Families (11)

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Publication number Priority date Publication date Assignee Title
WO1997015644A1 (en) * 1995-10-23 1997-05-01 Nsk Ltd. Lubricant composition
JP3687708B2 (en) * 1996-11-11 2005-08-24 日本精工株式会社 Grease composition for rolling device
GB2327944B (en) * 1997-08-06 2001-10-10 Ciba Sc Holding Ag Hetercyclic thioethers as additives for lubricants
JP4248688B2 (en) * 1999-06-29 2009-04-02 協同油脂株式会社 Grease composition for constant velocity joints
JP4567157B2 (en) * 2000-07-28 2010-10-20 協同油脂株式会社 Grease composition for constant velocity joints
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
JP4004276B2 (en) * 2001-11-21 2007-11-07 株式会社松村石油研究所 Grease composition
JP4272930B2 (en) * 2003-06-18 2009-06-03 昭和シェル石油株式会社 Urea grease composition for constant velocity joints
US7442673B2 (en) * 2003-08-15 2008-10-28 Crompton Corporation Reaction products of mercaptobenzothiazoles, mercaptothiazolines, and mercaptobenzimidazoles with epoxides as lubricant additives
JP4520756B2 (en) * 2004-02-26 2010-08-11 新日本石油株式会社 Grease composition for constant velocity joints
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008028955A2 *

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