EP3405555B1 - Grease composition - Google Patents

Grease composition Download PDF

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Publication number
EP3405555B1
EP3405555B1 EP17700854.7A EP17700854A EP3405555B1 EP 3405555 B1 EP3405555 B1 EP 3405555B1 EP 17700854 A EP17700854 A EP 17700854A EP 3405555 B1 EP3405555 B1 EP 3405555B1
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EP
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Prior art keywords
acid
water
grease
parts
mass
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EP17700854.7A
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German (de)
English (en)
French (fr)
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EP3405555A1 (en
Inventor
Keiji Tanaka
Yoshitomo Fujimaki
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/126—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 monocarboxylic
    • 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
    • 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
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2219/04—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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/069—Linear chain compounds
    • 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
    • C10N2030/26—Waterproofing or water resistance
    • 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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • This invention relates to a grease composition, and more specifically to a urea grease.
  • Japanese Laid-open Patent 2000-198994 has disclosed a water-resistant urea-based grease, to be used in environments where it is in contact with water, characterised in that the urea-based grease is made to contain 0.2 to 15 wt% of a metal salicylate of specific structure.
  • Japanese Laid-open Patent 2005-008745 has also disclosed a urea grease composition for use in constant velocity joints characterised in that the urea grease is made to contain a sulphurised molybdenum dialkyldithiocarbamate of specific structure, a triphenyl phosphorothionate of specific structure and a stearic acid metal salt.
  • This invention therefore, addresses this situation by offering a urea-based grease exhibiting a long-term water-resistant life while having superior water-resistant lubrication wear performance.
  • the present invention has been perfected by discovering that the above mentioned problems can be resolved by blending additives of three different kinds of constituents into a grease which uses a urea as a thickener.
  • Figure 1 is a drawing showing an outline of a water-resistant lubrication life test rig.
  • the grease composition pertaining to the present embodiment is a blend of specific additives to a urea grease.
  • a detailed explanation is given below of the specific constituents, amounts of each constituent, method of preparation, physical properties and applications of the grease composition in this embodiment.
  • base oil used in the grease composition of the present embodiment there is no special restriction on the base oil used in the grease composition of the present embodiment.
  • the mineral oils, synthetic oils and animal or plant oils used in normal grease compositions As specific examples mention may be made of those of Groups 1 to 5 of the base oil categories of the API (American Petroleum Institute). What is meant by an API base oil category here is a classification in a range of base oil materials as defined by the American Petroleum Institute in order to create guidelines for lubricating oil base oils.
  • paraffinic or naphthenic mineral oils obtained by means of one kind or a combination of two or more kinds of refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulphuric acid cleaning or clay treatment on lubricating oil fractions obtained by atmospheric distillation or vacuum distillation of crude oil.
  • PAO poly- ⁇ -olefin
  • oligomers hydrocarbon-based synthetic oils
  • a PAO is an ⁇ -olefin single polymer or copolymer.
  • the ⁇ -olefins are compounds having a C-C double bond at the terminals and examples are butene, butadiene, hexene, cyclohexene, methylcyclohexene, octene, nonene, decene, dodecene, tetradecene, hexadecene, octadecene and eicosene.
  • hydrocarbon-based synthetic oils examples include ethylene, propylene and single polymers or copolymers of isobutene. These compounds may be used singly or in mixtures of two or more kinds. Also, provided they have a C-C double bond at a terminal, these compounds may have whichever structure the isomer structure can take, and may have either a branched structure or a straight-chain structure. It is also possible to combine use of two or more kinds of these structural isomers or double-bond position isomers.
  • those more preferred for use are straight-chain olefins of carbon number 6 to 30, because the flash point is too low with a carbon number of 5 or less and the viscosity is too high, and so not practical, with a carbon number of 31 or higher.
  • GTL gas-to-liquid oils synthesised by the Fischer-Tropsch process which is a technology for producing liquid fuels from natural gas.
  • GTLs have a very low sulphur content and aromatic content, and a very high paraffin constituent ratio, so that they have superior oxidative stability and very small evaporation losses, which means they are ideal for possible use as a base oil in this invention.
  • urea thickener of the known art, there is no special restriction on the urea thickener used in the present embodiment, but ideally it will be a diurea thickener obtained by reacting 1 mol of a diisocyanate and 2 mol of a primary monoamine, a diurea thickener obtained by reacting 2 mol of a monoisocyanate and 2 mol of a primary diamine or a tetraurea thickener obtained by reacting 2 mol of a diisocyanate and 2 mol of a primary monoamine plus 1 mol of a primary diamine, or a triurea-monourethane thickener obtained by reacting 2 mol of a diisocyanate and 1 mol of a primary monoamine plus 1 mol of a primary diamine and further 1 mol of a higher alcohol.
  • a diurea or a tetraurea thickener is best. These may be used as one kind or in combinations of two or more kinds.
  • isocyanates which constitute the raw material, mention may be made of 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI) and octadecyl diisocyanate (ODI).
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • TODI 3,3'-dimethyl-4,4'-biphenylene diisocyanate
  • HDI hexamethylene diisocyanate
  • NDI naphthalene diisocyanate
  • ODI octadecyl diisocyanate
  • octylamine caprylamine
  • iso-octylamine laurylamine
  • myristylamine palmitylamine
  • stearylamine iso-stearlyamine
  • behenylamine oleylamine
  • linoleylamine beef tallow amine
  • coconut amine hydrogenated beef tallow amine
  • soybean amine cyclohexylamine
  • aniline p-chloroanaline
  • phenethylamine o-toluidine
  • m-toluidine p-toluidine
  • 2-naphthylamine 2-naphthylamine
  • diamines mention may be made of ethylenediamine, trimethylenediamine (propylenediamine), tetramethylenediamine (butylenediamine), pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine, and as salts thereof mention may be made of N-cocoalkyl-1,2-ethylenediamine, N-beef tallow alkyl-1,2-ethylenediamine, N-hardened beef tallow alkyl-1,2-ethylenediamine, N-cocoalkyl-1,3-propylenediamine, N-beef tallow alkyl-1,3-propylene diamine, N-hardened beef tallow
  • lauryl alcohol cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hexyldecanol, octyldodecanol and isostearyl alcohol.
  • thickeners other than urea compounds also possible to use thickeners other than urea compounds (other thickeners) together with the aforementioned thickener (urea) in the grease composition of the present embodiment.
  • these other thickeners mention may be made of tricalcium phosphate, alkali metal soaps, complex alkali metal soaps, alkaline earth metal soaps, complex alkaline earth metal soaps, alkali metal sulphonates, alkaline earth metal sulphonates, other metal soaps, metal terephthalate salts, monoureas, triurea-monourethanes, or polyureas other than diureas or tetraureas, or clays, silicas (silicon oxides) such as silica aerogels, and fluororesins such as polytetrafluoroethylene. These may be used as one kind or in combinations of two or more kinds. It is also possible to use any other substances apart from these which can impart a thickening effect to the liquid matter.
  • the grease composition of the present embodiment has specified additives (first, second and third constituents) added to the grease containing the aforementioned thickener (urea).
  • additives first, second and third constituents
  • urea thickener
  • the first additive constituent used in the present embodiment is an alkaline earth metal salicylate and/or an alkaline earth metal phenate.
  • alkaline earth metal salicylates As examples first of alkaline earth metal salicylates, mention may be made of the alkali metal salicylates known as metallic detergents.
  • Alkaline earth metal salts of alkylsalicylic acids are ideal.
  • salts of magnesium and/or calcium as the alkaline earth metal are ideal, and calcium salts in particular are ideal.
  • alkyl groups those of carbon number 4 to 30 are ideal, but 6 to 18 straight-chain or branched alkyl groups are even better.
  • these may be straight-chain or branched and they may be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.
  • alkaline earth metal phenates mention may be made of the alkali metal salicylates known as metallic detergents, and mention may be made of alkaline earth metal salts of alkylphenols, alkylphenol sulphides and alkylphenol Mannich reaction products, and especially the magnesium salts and/or calcium salts. Calcium salts in particular are ideal.
  • the alkaline earth metal salicylate and/or alkaline earth phenate based metallic detergents are preferably metallic detergents having a total base number (BN) as stipulated in JIS K2501 (perchloric acid titration) of 5 to 600 mg KOH/g, but more preferably metallic detergents of 50 to 500 mg KOH/g, and still more preferably metallic detergents of 100 to 400 mg KOH/g. If the BN is within this range, should there be ingress of water into the urea grease of this invention, it will disperse more homogeneously in the base oil and will be more likely to maintain this state.
  • BN total base number
  • JIS K2501 perchloric acid titration
  • the action will be to make further improvements in respect of the occurrence of rust and reduction of lubricity associated with the weakening and softening of the grease structure due to the influence of the water and also with free water due to insufficient moisture dispersion.
  • the additive constituents of the metallic detergents may also contains salts of organic acids of one type or salts or organic acids of more than one type, and these may also be mixtures of neutral metallic detergents, overbased metallic detergents or both.
  • the second additive constituent used in the present embodiment is a metal soap, specifically a stearic acid metal salt.
  • a metal soap specifically a stearic acid metal salt.
  • the non-aqueous stearic acid metal salt here, mention may be made of salts of alkali metals (for example, lithium), alkaline earth metals (for example, magnesium, calcium or barium), aluminium and zinc. Special preference is given to the use of calcium and/or magnesium salts.
  • Said constituent may be used as one kind or as a combination of a plurality of kinds.
  • the third additive constituent used in the present embodiment is a calcium sulphonate and/or a zinc naphthenate.
  • the calcium sulphonate first is an ordinary calcium sulphonate, and as examples mention may be made of calcium salts of petroleum sulphonic acids, calcium salts of alkylaromatic sulphonic acids, overbased calcium salts of petroleum sulphonic acids and overbased calcium salts of alkyl aromatic sulphonic acids. Said constituents may be used singly or in mixtures.
  • the zinc naphthenate next is an ordinary zinc naphthenate, and as examples mention may be made of complex mixtures of naphthenic acid derived from selected crude oil fractions, ordinarily by reacting those fractions with a sodium hydroxide solution and then acidifying and refining them.
  • the molecular weight of the naphthenic acid before the reaction with the zinc compound is preferably in the range 150 to 500, but more preferably 180 to 330.
  • additives such as freely chosen anti-oxidants, rust preventatives, oiliness agents, extreme pressure additives, anti-wear agents, solid lubricants, metal deactivators, polymers, non-metallic detergents, colourants and water repellents, the total amount of the freely chosen constituents, taking the total amount of the grease composition as 100 parts by mass, being approximately 0.1 to 20 parts by mass.
  • anti-oxidants are 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-para-cresol, p,p'-dioctyldiphenylamine, N-phenyl- ⁇ -naphthylamine or phenothiazine.
  • rust preventatives are paraffin oxide, carboxylic acid metal salts, sulphonic acid metal salts, carboxylate esters, sulphonate esters, salicylate esters, succinate esters, sorbitan esters and various amine salts.
  • oiliness agents and extreme pressure additives plus anti-wear agents include sulphurised zinc dialkyldithiophosphates, sulphurised zinc diaryldithiophosphates, sulphurised zinc dialkyldithiocarbamates, sulphurised zinc diaryldithiocarbamates, sulphurised molybdenum dialkyldithiophosphates, molybdenum diaryldithiophosphates, sulphurised molybdenum dialkyldithiocarbamates, sulphurised molybdenum diaryldithiocarbamates, organomolybdenum complexes, sulphurised olefins, triphenyl phosphate, triphenyl phosphorothionate, tricresyl phosphate, other phosphate esters and sulphurised oils and fats.
  • solid lubricants include molybdenum disulphide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene), tungsten disulphide and graphite fluoride.
  • metal deactivators mention may be made of N,N'-disalicylidene-1,2-diaminopropane, benzotriazoles, benzoimidazoles, benzothiazoles and thiadiazoles.
  • polymers mention may be made of polybutenes, polyisobutenes, polyisobutylenes, polyisopropenes and polymethacrylates.
  • non-metallic detergents mention may be made of succinimides.
  • the grease composition of the present embodiment ideally contains alkyl organic acids and/or alkyl organic acid esters.
  • alkyl organic acids or alkyl organic acid esters mention may be made of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid (heptanoic acid), capric acid, 2-ethylhexanoic acid, pelargonic acid, undecylic acid, lauric acid, linderic acid, tridecylic acid, myristic acid, tsuzuic acid, physetoleic acid, myristoleic acid, pentadecylic acid, palmitic acid, palmitoylic acid, margaric acid, stearic acid, isostearic acid, petrosilinic acid, elaidic acid, oleic acid, vaccenic acid, linolic acid
  • Grease composition (amounts of each constituent in the blend)
  • the amount of base oil in the blend taking the total amount of the grease composition as 100 parts by mass, will be preferably 50 to 95 parts by mass, but more preferably 60 to 90 parts by mass and yet more preferably 70 to 85 parts by mass.
  • the total amount of thickeners in the blend taking the total amount of the grease composition as 100 parts by mass, will be preferably 3 to 50 parts by mass, but more preferably 5 to 40 parts by mass and yet more preferably 7 to 30 parts by mass.
  • the amount of the aforementioned urea compound in the blend, taking the total amount of the grease composition as 100 parts by mass is 0.5 to 50 parts by mass. If the amount of the aforementioned urea in the blend is less than 0.5 parts by mass, it will become difficult to maintain sufficient hardness as a grease, and it will be prone to seep from the lubrication points no matter how much ingress of water there is, so that the targeted lubrication performance cannot be displayed. If there is more than 50 parts by mass, the grease will become too hard and the supply of base oil will be insufficient, so that there will be a likelihood of a reduction in lubrication performance. Costs will also rise.
  • the incorporated amount of alkaline earth metal salicylate and/or alkaline earth metal phenate metallic detergent which is the first additive constituent, taking the total grease composition as 100 parts by mass, is 0.1 to 10 parts by mass, but more preferably 0.3 to 7 parts by mass, and yet more preferably 0.5 to 5 parts by mass. If the amount of metallic detergent is less than 0.1 part by mass, although this will not impact on the hardness of the grease (it will not cause it to soften), it will not be possible sufficiently to disperse particles of water that have been mixed in the grease, and it may be difficult to maintain a stable lubricating film.
  • the incorporated amount of metal soap being a non-aqueous stearic acid metal salt, which is the second additive constituent, taking the total grease composition as 100 parts by mass, is 0.1 to 10 parts by mass, but more preferably 0.3 to 7 parts by mass, and yet more preferably 0.5 to 5 parts by mass. If the amount of metal soap is less than 0.1 part by mass, it will not be possible sufficiently to disperse particles of water that have been mixed in the grease, and it may be difficult to maintain a stable lubricating film. If it is greater than 10 parts by mass, although this will improve dispersion of the water, costs will simply rise and no further effect can be expected.
  • the incorporated amount of calcium sulphonate and/or naphthenate, which is the third additive constituent, taking the total grease composition as 100 parts by mass, is 0.1 to 10 parts by mass, but more preferably 0.3 to 7 parts by mass, and yet more preferably 0.5 to 5 parts by mass. If the amount of these additives is less than 0.1 part by mass, it may become difficult to exhibit the above mentioned effects, and if it is greater than 10 parts by mass, inhibition of the occurrence of rust can be expected but the grease will become prone to seep out from lubrication points because of shearing, so that it may become difficult to obtain the targeted lubrication performance.
  • the grease composition of the present embodiment will preferably have a penetration of No. 00 to No. 4 (175 to 430), but more preferably a penetration of No. 2 to No. 3 (220 to 295).
  • the penetration expresses the visual hardness.
  • the values used here for penetration are for worked penetration as measured in accordance with JIS K 2220 7.
  • the grease composition of the present embodiment has no correlation with the dropping point in terms of performance, but as a criterion for the structure of the urea grease thickener to achieve proper cohesion, it is preferably not less than or in excess of 180°C.
  • the dropping point refers to the temperature at which a viscous grease loses the structure of the thickener as the temperature goes on rising. Measurement of the dropping point here is done in accordance with JIS K 2220 8.
  • the grease composition of the present embodiment will preferably have a post-test penetration of not more than 395, and the difference between before the test and after the test will be not more than 90, but more preferably the post-test penetration will be not more than 355 and the difference between before the test and after the test will be not more than 70. If the post-test penetration exceeds 395, grease will become prone to leak out from the lubrication points of bearings and the like, and it may become impossible to supply lubricating grease to rubbing or sliding parts.
  • Shear stability with contained water is determined in accordance with the roll stability test stipulated in ASTM D1831. Specifically, 10% by internal proportion of distilled water is blended with a pre-supplied grease (10% water to 90% grease) and made to disperse uniformly. 50 g of this grease is weighed out and supplied to the roll stability test, where shear is applied for 24 hours at 40°C. The grease is then removed and the worked penetration at 25°C is measured. To obtain the test's before-and-after penetration, the value of the penetration before the test is subtracted from the penetration after the test.
  • the lubrication life in a water-resistant lubrication life test of the grease composition of the present embodiment is preferably not less than 180 hours, but more preferably not less than 240 hours and yet more preferably not less than 300 hours.
  • the procedure for the water-resistant lubrication life test is as follows.
  • Figure 1 shows the outline of the water-resistant lubrication life test apparatus. As shown in said drawing, the test apparatus is designed to evaluate the lubrication life of a bearing while water is injected into the grease. This procedure is an improved version of the water-rinse water-resistance test apparatus stipulated in JIS K 2220 5.12.
  • circulating water is not sprayed (300 ml/min) into the bearing outer wheel guard (seal plate) of the test ball bearing as in the JIS, but distilled water is injected into the grease directly inside the housing, which means that it is possible to inject a more precise amount of water, which improves the reliability of the test and allows the lubrication life to be measured as accurately as possible.
  • 5.0 g of sample grease is packed into the test bearing and the bearing is installed in the housing, after which 100 ml of distilled water heated to 40°C is injected into the housing each minute, whilst running at 3,000 rpm. The injected water is discharged to the outside via the inside of the test bearing.
  • this is taken to be the time for the bearing to reach a high torque because of unsatisfactory lubrication by the supplied grease, for the brake mechanism to actuate when the electric current of the motor which drives the bearing has exceeded 200% of the current in stable operation, and for the drive motor to come to a stop.
  • the weight of the bearing before and after the test is also taken and calculated as the amount of wear of the bearing.
  • the grease composition of the present embodiment can of course be used in machinery, bearings and gears generally, but it can also exhibit superior performance in environments that are more severe for grease lubrication, for example in applications where there is the possibility of water ingress.
  • it is ideal for use in the lubrication of water pumps, cooling fan motors, starters, alternators and various actuator parts in the engine area, propeller shafts, constant velocity joints (CVJ), wheel bearings and clutches in the power train, and various other parts such as electric power steering (EPS), electric powered windows, damping devices, ball joints, door hinges, handles and brake expanders.
  • EPS electric power steering
  • Base oil A Mixture, in the proportions of 80 parts by mass to 20 parts by mass, of a paraffinic mineral oil obtained by dewaxing and solvent refining and belonging to Group 1 of the API (American Petroleum Institute) classification (kinematic viscosity at 100°C 11.25 mm 2 /s, viscosity index 97) and a naphthenic mineral oil belonging to Group (kinematic viscosity at 100°C 10.71 mm 2 /s, viscosity index 30).
  • API American Petroleum Institute
  • Tests were carried on the examples of embodiment and comparative examples, by the above mentioned test methods, in respect of dropping point, worked penetration, roll stability test and water-resistant lubrication life.
  • the properties of the various greases of the examples of embodiment and comparative examples obtained are shown in Table 1.
  • the worked penetration of the greases of the examples of embodiment and comparative examples was in every case No. 2 or No. 2.5 penetration.
  • the dropping point for all the greases was not less than 220°C, values not at all inferior for urea greases.
  • As to the criterion of water resistance an evaluation was made on the basis of the results of a roll stability test, performed with samples mixed with 10% water in the grease, and a water-resistant lubrication life test.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP17700854.7A 2016-01-22 2017-01-20 Grease composition Active EP3405555B1 (en)

Applications Claiming Priority (2)

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JP2016011009A JP6683484B2 (ja) 2016-01-22 2016-01-22 グリース組成物
PCT/EP2017/051242 WO2017125581A1 (en) 2016-01-22 2017-01-20 Grease composition

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EP3405555B1 true EP3405555B1 (en) 2021-09-15

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CN108865373B (zh) * 2018-08-05 2021-08-17 杭州新港润滑科技有限公司 一种复合磺酸钙聚脲混合润滑脂及其制备方法
CN112574797B (zh) * 2020-12-16 2022-03-04 正大国际科技(常德)集团有限公司 一种气凝胶负载型植物基润滑油添加剂及其制备方法和应用
FR3129948B1 (fr) * 2021-12-06 2024-08-30 Totalenergies Marketing Services Graisses lubrifiantes conductrices.
FR3129949B1 (fr) * 2021-12-06 2024-08-30 Totalenergies Marketing Services Graisses lubrifiantes conductrices.
CN115247094A (zh) * 2022-08-12 2022-10-28 福建优立盛油脂有限公司 一种聚脲-无水钙基润滑脂及其制备方法

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JPS60149696A (ja) * 1984-01-13 1985-08-07 Idemitsu Kosan Co Ltd グリ−ス組成物
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JP4634585B2 (ja) * 2000-08-10 2011-02-16 昭和シェル石油株式会社 防錆性および耐摩耗性が改良されたグリース組成物
JP4641336B2 (ja) * 2000-08-10 2011-03-02 協同油脂株式会社 グリース組成物
JP2003342593A (ja) * 2002-05-29 2003-12-03 Nsk Ltd グリース組成物及び転がり軸受
JP4112419B2 (ja) * 2003-04-24 2008-07-02 協同油脂株式会社 グリース組成物
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JP4474679B2 (ja) * 2004-01-27 2010-06-09 Ｊｆｅスチール株式会社 グリース組成物及び軸受
EP1770309A4 (en) * 2004-06-23 2011-10-05 Nsk Ltd TORQUE DEVICE WITH INTEGRATED ONE-WAY COUPLING
EP1806391A1 (en) * 2004-10-18 2007-07-11 NSK Ltd. Waterproof grease composition and roller bearing for wheel support
CN101044232A (zh) * 2004-10-18 2007-09-26 日本精工株式会社 耐水性润滑油组合物以及车轮支撑用滚动轴承
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JP2017128702A (ja) 2017-07-27
CN108473909A (zh) 2018-08-31
BR112018014800A2 (pt) 2018-12-18
BR112018014800B1 (pt) 2022-03-22
CN108473909B (zh) 2022-04-19
EP3405555A1 (en) 2018-11-28
KR20180101405A (ko) 2018-09-12
JP6683484B2 (ja) 2020-04-22
US20210171858A1 (en) 2021-06-10
WO2017125581A1 (en) 2017-07-27

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