WO2013017528A1 - Composition de graisse - Google Patents

Composition de graisse Download PDF

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Publication number
WO2013017528A1
WO2013017528A1 PCT/EP2012/064719 EP2012064719W WO2013017528A1 WO 2013017528 A1 WO2013017528 A1 WO 2013017528A1 EP 2012064719 W EP2012064719 W EP 2012064719W WO 2013017528 A1 WO2013017528 A1 WO 2013017528A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
grease composition
grease
urea
Prior art date
Application number
PCT/EP2012/064719
Other languages
English (en)
Inventor
Takahiro Ozaki
Tetsuya Kato
Original Assignee
Shell Internationale Research Maatschappij B.V.
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Publication date
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Publication of WO2013017528A1 publication Critical patent/WO2013017528A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C10M2201/0856—Phosphorus oxides, acids or salts used as thickening agent
    • 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
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products 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
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for 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. More specifically, it relates to a grease composition having thermal stability and oxidative stability.
  • synthetic oils are used as the base oils for grease lubricants, and for thickeners use is made of calcium soaps, lithium soaps, calcium complex soaps, calcium sulphonate-based types, lithium complex soaps, aluminium complex soaps, clays, silica gels, urea compounds, sodium terephthalamates , fluorine resins and so on.
  • urea greases which use urea-based thickeners, have superior thermal stability and oxidative stability, and it is known that compared to greases using metallic soap-based thickeners, bearings packed with urea greases exhibit longer life at high temperatures. In many cases anti-oxidants are incorporated but the superior thermal stability and oxidative stability of these urea greases is attributable mainly to the urea-based
  • the aim of the present invention is to offer a grease composition which has little change in state such as hardening or liquefaction even at high temperatures and which is superior by virtue of its oxidative
  • a grease composition constituted by mixing 60 to 95 parts by weight of base oil, 3 to 25 parts by weight of a urea-based thickener and 0.05 to 5 parts by weight of a hindered amine-based anti-oxidant, taking the total composition as 100 parts by weight.
  • the grease composition of this invention is one having superior thermal stability and oxidative stability under high temperatures, and it is capable of performing a function as lubricating agent under a wide range of temperatures which include the high-temperature domain.
  • the grease composition of this invention contains a base oil, a thickener and an anti-oxidant .
  • An explanation is given below in turn for each component in the grease composition, the amount of each component in the grease composition, the method of manufacture of the grease composition, the characteristics of the grease
  • the base oil used in the grease composition of this invention it is possible to use the mineral oils, synthetic oils, animal oils, plant oils or mixtures thereof normally used for lubricating oils.
  • Their kinematic viscosity at 100°C should preferably be approximately 2 to 40 mm 2 /s. In particular, it is
  • base oils which belong to Group I, Group II, Group III and Group IV of the API (American Petroleum Institute) base oil
  • Group I base oils include, for example, paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as solvent refining, hydrorefining, and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Group II base oils include, for example, paraffinic mineral oils obtained by
  • Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of not more than 5% and so are suitable for use in this invention.
  • Group III and Group 11+ base oils include, for example, paraffinic mineral oils manufactured by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by
  • synthetic oils mention may be made of polyolefins, dibasic acid diesters such as dioctyl sebacate, polyol esters, alkylbenzenes ,
  • alkylnaphthalenes esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyldiphenyl ethers, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins and the like) and silicones.
  • the aforementioned polyolefins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and a-olefins with five or more carbons. In the manufacture of polyolefins, one kind of the
  • olefins may be used singly or two or more kinds may be used in combination.
  • Particularly suitable are the polyolefins called poly-a-olefins (PAO) .
  • PAO poly-a-olefins
  • GTLs gas to liquid synthesised by the Fischer- Tropsch method of converting natural gas to liquid fuel have a very low sulphur content and aromatic content compared with mineral oil base oils refined from crude oil and have a. very high paraffin constituent ratio, and so have excellent oxidative stability, and because they also have extremely small evaporation losses, they are suitable as base oils for this invention.
  • thickeners used in this invention, but from the standpoint of oxidative stability and bearing life at high temperatures and from the standpoint of effect in preventing damage to machine parts they will include as an essential
  • urea-based thickener constituents a urea-based thickener, and as optional constituents they may also include tricalcium phosphates, soap-based thickeners, bentones or silica gels and the like.
  • These thickeners are preferably those in which the dropping point of the grease composition is not less than 200°C, and more preferably those where it is not less than 250°C. This is because, if the dropping point of the grease composition is at least 250°C, it will inhibit the possible occurrence of lubrication problems such as softening at high temperatures and leakage or seizure accompanying that.
  • urea-based thickeners used in this invention refer to all thickeners which contain urea bonds, and these urea bonds in general are obtained by reacting amines with isocyanates.
  • urea-based thickeners mention may be made of monourea-based
  • Diurea compounds such as monourea and monourea-monourethane, diurea-based compounds such as diurea, diurea- monourethane and diurea-diurethane, and polyurea-based compounds such as triurea, triurea-monourethane, triurea- diurethane, triurea-triurethane, tetraurea, tetraurea- monourethane, tetraurea-diurethane, tetraurea-triurethane and tetraurea-tetraurethane, but there is no particular limitation .
  • Diurea compounds are obtained, for instance, by a reaction between a diisocyanate and a monoamine.
  • diisocyanates mention may be made of tolylene diisocyanate, bitolylene diisocyanate, m-xylene
  • dodecylamine hexadecylamine, octadecylamine, oleylamine, aniline, p-chloroaniline, benzylamine, m-xylidine, p- toluidine, o-toluidine, cyclohexylamine and
  • Polyurea compounds are obtained, for instance, by a reaction of diisocyanates with diamines and monoamines.
  • diisocyanates and monoamines mention may be made of the same ones used for the production of diurea compounds, and for diamines mention may be made of ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, phenylene diamine, tolylene diamine and xylylene diamine.
  • compounds containing urethane bonds in addition to urea bonds can be obtained by reacting an alcohol with an isocyanate.
  • the alcohols mention may be made of octyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol and eicosine alcohol.
  • alkyldiureas obtained by reaction of diisocyanates and alkylmonoamines are preferred.
  • thickeners with the aforementioned urea-based thickeners in the grease composition of this invention.
  • other thickeners mention may be made of calcium triphosphates, alkali metal soaps, alkali metal complex soaps, alkaline earth soaps, alkaline earth complex soaps, alkali metal sulphonates, alkaline earth metal sulphonates, other metal soaps, metal terephthalamate salts, clays, silicas such as silica aerogels ⁇ silicate- based) and fluorine resins such as
  • polytetrafluoroethylene and these may be used as one kind or as combinations of two or more kinds. Apart from these, it is also possible to use any of those which are capable of contributing a thickening effect to a liquid substance.
  • Ca(OH)2 As regards grain size, use is normally possible so long as the grains are not more than approximately ⁇ average diameter, but a diameter of not more than 20 ⁇ is preferred and a diameter of not more than ⁇ is especially preferred. In this invention wherever content is shown it will be shown as mass based on [Ca 3 (P0 4 ) 2 ]3 ⁇ Ca(OH)2- Also, for alkali metal soaps or alkaline earth metal soaps mention may be made in general of those obtained by reaction of alkali metal hydroxides or alkaline earth metal hydroxides with fatty acids, and these fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid and eicosanoic acid.
  • alkali metals mention may be made of lithium, sodium and potassium, and as examples of alkaline earth metals mention may be made of calcium and magnesium.
  • alkali metal soaps thereof mention may be made of lithium soaps, lithium complex soaps, sodium soaps, sodium complex soaps, potassium soaps and potassium complex soaps, and also as examples of alkaline earth metal soaps mention may be made of calcium soaps, calcium complex soaps, magnesium soaps, magnesium complex soaps, barium soaps and barium complex soaps.
  • other metal soaps mention may be made of aluminium soaps and aluminium complex soaps.
  • Complex soaps are those which contain a second metal salt of an acid in complex form in metals soaps of the aforementioned fatty acids.
  • lithium complex soaps mention may be made of those which contain a second metal salt of an acid in addition to the lithium salt of the fatty acid.
  • aluminium complex soaps mention may be made specifically of aluminium stearate benzoate.
  • the aforementioned terephthalamate metal salts mention may be made of sodium terephthalamates and lithium terephthalamates, but sodium terephthalamates are preferably used.
  • Anti-oxidants are included in the grease composition of this invention with a view to stabilising it against oxidation.
  • a hindered amine-based anti-oxidant is used as an essential constituent, and it is more preferable to combine it with use of a hindered phenol-based antioxidant .
  • hindered amine-based antioxidants used in this invention mention may be made of tetrakis (2,2,6, 6-tetramethyl ⁇ 4-piperidyl) 1,2,3,4- butanetetracarboxylate, (2,2,6, 6TMtetramethyl ⁇ -4 ⁇ - piperidyl) -1,2,3, -butanetetracarbox late, bis (2, 2, 6, 6- tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6- pentamethyl-4-piperidyl) sebacate and decane diacid bis (2, 2, 6, 6-tetramethyl-l (octyloxy) -4-piperidinyl ester.
  • hindered phenol-based antioxidants used in this invention mention may be made of octadecyl-3- (3, 5-di ⁇ t-butyl ⁇ 4 ⁇ hydroxyphenyl) propionate, pentaerythrityl ⁇ tetrakis [3- (3, 5-di-t-butyl-4- hydroxyphenyl ⁇ propionate], 2, -bis- (n-octylthio) -6TM (4- hydroxy-3, 5-di-t-butylanilino) ⁇ 1, 3, 5-triazine, 1,3,5- trimethyl-2, 4, 6-tris (3, 5-di-t-butyl- ⁇ 4-hydroxybenzyl ) benzene, triethylene glycol-bis- [3- ( 3-t-butyl-5-methyl-4- hydroxyphenyl) propionate], 1 , 6TMhexanediol-bis [ 3- ( 3 , 5 ⁇ di- t-butyl-4-hydroxyphenyl)
  • hindered amine-based anti-oxidants As well as the aforementioned hindered amine-based anti-oxidants and hindered phenol-based anti-oxidants, it is possible to combine their use with other anti-oxidants (such as zinc dithiophosphates, dithiocarbamic acid-based types, ashless dithiocarbamates, benzimidazole-based types, phosphorous acid-based types and organothio acid- based types) .
  • dithiocarbamic acid-based types mention may be made of nickel
  • Benzimidazole-based types include 2-mercaptobenzimidazole .
  • phosphorous acid-based types mention may be made of tris (nonylphenyl) phosphite and trioctadecyl phosphite.
  • organothio acid-based types mention may be made of dilaurylthiodipropionate,
  • the a orementioned antioxidants may be used alone or combined as a plurality. Apart from the above-mentioned constituents, it is possible to add to the grease composition of this
  • invention optional additives such as rust preventatives, extreme pressure agents, metal deactivators, metallic detergents, non-metallic detergents, defoamers, viscosity increasing agents, colorants and water repellants.
  • rust preventatives mention may be made of metallic sulphonates and succinate esters.
  • metallic detergents mention may be made of metal
  • sulphonates metal salicylates and metal phenates.
  • non-metallic detergents mention may be made of succinate imides .
  • metal deactivators mention may be made of benzotriazoles and thiadiazoles .
  • defoamers mention may be made of methyl silicones, dimethyl silicones, fluorosilicones and polyacrylates .
  • the amount of base oil in the blend is preferably 60 to 95 parts by weight and more preferably 70 to 90 parts by weight.
  • the amount of urea thickener in the blend is preferably 3 to 25 parts by weight, more preferably 5 to
  • thickeners such as tricalcium phosphates, soap-based thickeners, bentones or silica gels
  • thickeners may be added as necessary. If added, they may each be blended in the amount, taking the total grease composition as 100 parts by weight, of preferably 0.05 to 30 parts by weight, but more preferably 0.01 to 20 parts by weight and even more preferably 1 to 10 parts by weight.
  • the total amount of both types taking the total grease composition as 100 parts by weight, comprises 3 to 40 parts by weight, and more preferably 5 to 20 parts by weight.
  • the amount of hindered amine-based anti-oxidants used in the blend, taking the total grease composition as 100 parts by weight, is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 4.0 parts by weight, and even more preferably 0.2 to 2.0 parts by weight.
  • Hindered phenol-based anti-oxidants may also be used in addition to the hindered a ine-based anti-oxidants and, taking the total grease composition as 100 parts by weight, will be used in the amount of preferably 0.05 to 5 parts by weight, more preferably 0.07 to 2.5 parts by weight, and even more preferably 0.08 to 2.25 parts by weight.
  • the total amount used in the blend when hindered amine-based anti-oxidants are used together with hindered phenol- based anti-oxidants, taking the total grease composition as 100 parts by weight, will preferably be 0.1 to 8.0 parts by weight, more preferably 0.15 to 6.0 parts by weight, and even preferably 0.20 to 4.0 parts by weight.
  • both hindered amine-based anti-oxidants and hindered phenol-based anti-oxidants it is possible to use them in an optional weight ratio of hindered amine- based anti-oxidants : hindered phenol-based antioxidants, for example and preferably 5:1 to 1:5, but more preferably 3:1 to 1:3 and even more preferably 4:1 to
  • the aforementioned optional additives may be used in any amount as required insofar as they have the objective and effect of the invention.
  • the grease composition of this invention may be manufactured by the methods of manufacturing grease that are generally used. For example, an isocyanate compound and an amine compound are dissolved in a base oil heated to 50°C, and through further heating and agitation a urea compound, being a thickener, is produced in the base oil. After heating to 165°C and holding for 1 hour, a hindered amine-based thickener and optionally also a hindered phenol-based thickener are added, and by agitation, mixing, cooling to room temperature and finishing by means of a three-roll mill or the like, the desired urea grease can be obtained.
  • aforementioned other thickeners have been added to a base oil.
  • the grease composition of the invention by mixing together in suitable proportions a grease composition which contains a urea-based thickener and anti-oxidants in a base oil and a lubricant composition which contains mainly another thickener in a base oil. It is possible to obtain a grease composition with a high thermal stability at high temperatures as in the invention by any of the
  • the grease composition of this invention is believed to have high thermal stability and oxidative stability because the state of the grease is stable even at high temperatures and the hue changes are also extremely small.
  • the grease composition of this invention preferably satisfies at least one of the following (1), (2) and (3 ⁇ , and more preferably all of them.
  • the percentage change in evaporation is not more than 25% and the increase in CO (carbonyl group)
  • absorption is not more than 35%.
  • the grease composition of this invention can be used not only for applications in generally used machinery, bearings and gears but it can also exhibit superior performance under more rigorous load conditions. For example, it can be satisfactorily used for the
  • machinery such as power shovels, bulldozers and crane trucks, steelmaking, paper mills, timber-making
  • Evaporation (%) (weight (g) before heating test - weight (g) after heating test) / (weight (g) before heating test) x 100
  • a (absorption ratio of grease before heating test) (absorption at 1710cm -1 ⁇ / (absorption at 720cm "1 )
  • Thickener B Taihei Chemical Industries Ltd, tricalcium phosphate
  • Base oil A A paraffinic mineral oil obtained by solvent dewaxing refining and belonging to Group I. The kinematic viscosity at 100°C was 11.25mm 2 /s and the viscosity index was 97.
  • Base oil B A poly-a-olefin and belonging to Group IV. The kinematic viscosity at 100°C was 6.34mm 2 /s and the viscosity index was 136.
  • Base oil C A paraffinic mineral oil manufactured by a high degree of hydrorefining and belonging to Group
  • the kinematic viscosity at 100°C was 7.603mm 2 /s and the viscosity index was 128.
  • Base oil D A GTL (gas to liquid) synthesised by the Fischer-Tropsch method and belonging to Group III.
  • the kinematic viscosity at 100°C was 7.77mm 2 /s
  • the kinematic viscosity at 40°C was 43.88mm 2 /s @
  • the viscosity index was 148.
  • Anti-oxidant A Tetrakis (2 , 2 , 6, 6-tetramethyl-4- piperidyl-1, 2, 3, 4-butane tetracarboxylate (trade name:
  • Anti-oxidant B Octadecyl-3- ( 3, S-di-t-butyl ⁇ 4 ⁇ hydroxyphenyl) propionate (trade name: Adeka AIN-100, hindered phenol-based anti-oxidant)
  • Anti-oxidant C Pentaerythrityl-tetrakis [3 ⁇ ( 3, 5-di- t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox L101, hindered phenol-based anti-oxidant)
  • Anti-oxidant D 2 , -bis- (n-octylthio) -6- (4-hydroxy- 3, 5-di-t-butylanilino) -1, 3, 5-triazine (trade name:
  • Anti-oxidant E 1 , 3, 5-trimethyl-2 , 4 , 6-tris ⁇ 3,5- di- t ⁇ b tyl-4- hydroxybenzyl) benzene (trade name: Irganox 1330: hindered phenol-based anti-oxidant)
  • Anti-oxidant F p, ' -dioctyldiphenylamine (trade name: Vanlube 81, aromatic amine-based anti-oxidant)
  • Anti-oxidant G Styrenated diphenylamine (trade name: Stearer-LAS, aromatic amine-based anti-oxidant) Preparation of examples of embodiment and
  • MDI (16.52g, 0.066 mole) with caprylylamine (17.08g, 0.132 mole) in 688g of Base oil A at approximately 50°C
  • MDI 31.60g, 0.126 mole
  • laurylamine 46.80g, 0.253 mole
  • heating was carried out up to approximately 165°C. This was maintained for 1 hour while agitating.
  • the anti-oxidants specified in Table 1 were added and mixed in according to the recipes for the examples of embodiment and comparative examples. After cooling to room temperature, a finishing treatment was carried out using a three-roll mill and the target greases were obtained.
  • Example of Embodiment 11 and Comparative Example 5 (Amount of urea thickener: 10%, CAP: 5.0%) 400 g of the base grease in Example of Embodiment 1, before anti-oxidants were added (amount of urea thickener 14.0%), was diluted with 160 g of base oil heated to approximately 120°C, so that the amount of urea thickener was made 10%. Then a grease was obtained in which
  • a commercial mineral oil-based urea grease (trade name: Shell Stamina Grease RL2) was used.
  • the percentage change in penetration before and after the heating test in the examples of embodiment was less than 50%, and so they were not prone to hardening by heat, which was desirable.
  • the grease compositions of Comparative Examples 1 and 6 were also below 50%, but the grease compositions of Comparative Examples 2 to 5 had a change in penetration that exceeded 50%, and so their stability as greases in respect of high temperatures was not at all satisfactory,
  • the amount of evaporation of the grease compositions of the examples of embodiment was good, at less than 25%, but for all the grease compositions of the comparative examples it exceeded 25%, which cannot be described as good.
  • the absorption ratios of all the grease compositions of the examples of embodiment was under 0.300 but for all the grease compositions of the comparative examples it was seen to exceed 0.300, and so a relative gap in oxidative stability after heating was discernible.
  • the increase in absorption when a comparison was made before and after heating, whereas it was less than 35% for all the grease compositions of the examples of embodiment, the grease compositions of the comparative examples exceeded 60% and so a large variation before and after heating was discerned.
  • the grease composition of the invention which thus takes a base oil, a urea-based thickener and a hindered amine anti-oxidant , and preferably also a hindered phenol anti-oxidant, as essential constituents, has little thermal hardening, has low evaporation and has the small absorption typical of carbonyl groups, and further has little change in hue of the grease after heating, which means that it has excellent thermal stability and

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Composition de graisse qui, si l'on considère que son tout représente 100 parties en poids, est obtenue par mélange de 60 à 95 parties en poids d'une huile de base, 3 à 25 parties en poids d'un épaississant à base d'urée et 0,05 à 5 parties en poids d'un antioxydant à base d'une amine encombrée. La composition de graisse décrite fait preuve d'un faible changement d'état, même sous des températures élevées, et offre une stabilité à l'oxydation supérieure.
PCT/EP2012/064719 2011-07-29 2012-07-26 Composition de graisse WO2013017528A1 (fr)

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Cited By (1)

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US9872910B2 (en) 2014-07-11 2018-01-23 Fujifilm Corporation Aqueous ophthalmic composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11767488B2 (en) * 2017-12-25 2023-09-26 Nsk Ltd. Lubricant composition and rolling bearing having same sealed therein
JP7455376B2 (ja) 2020-06-29 2024-03-26 株式会社ニッペコ グリース組成物

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US5268113A (en) * 1989-07-07 1993-12-07 Ciba-Geigy Corporation Lubricant composition
EP0714975A1 (fr) * 1994-12-02 1996-06-05 Showa Shell Sekiyu Kabushiki Kaisha Composition de graisse lubrifiante
JP2004359809A (ja) 2003-06-04 2004-12-24 Nsk Ltd グリース組成物及び転がり軸受
JP2007037322A (ja) 2005-07-28 2007-02-08 Oriental Motor Co Ltd 永久磁石式回転子
JP2007077244A (ja) 2005-09-13 2007-03-29 Nsk Ltd グリース組成物及び転がり軸受
EP1930400A1 (fr) * 2005-09-29 2008-06-11 Idemitsu Kosan Co., Ltd. Composition lubrifiante

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JP4946063B2 (ja) * 2006-01-12 2012-06-06 日本精工株式会社 グリース組成物及び転がり軸受
JP5283427B2 (ja) * 2008-05-16 2013-09-04 株式会社Ａｄｅｋａ グリース組成物
JP5407312B2 (ja) * 2008-12-10 2014-02-05 日本精工株式会社 グリース組成物及び転がり軸受

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Publication number Priority date Publication date Assignee Title
US5268113A (en) * 1989-07-07 1993-12-07 Ciba-Geigy Corporation Lubricant composition
EP0714975A1 (fr) * 1994-12-02 1996-06-05 Showa Shell Sekiyu Kabushiki Kaisha Composition de graisse lubrifiante
JP2004359809A (ja) 2003-06-04 2004-12-24 Nsk Ltd グリース組成物及び転がり軸受
JP2007037322A (ja) 2005-07-28 2007-02-08 Oriental Motor Co Ltd 永久磁石式回転子
JP2007077244A (ja) 2005-09-13 2007-03-29 Nsk Ltd グリース組成物及び転がり軸受
EP1930400A1 (fr) * 2005-09-29 2008-06-11 Idemitsu Kosan Co., Ltd. Composition lubrifiante

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9872910B2 (en) 2014-07-11 2018-01-23 Fujifilm Corporation Aqueous ophthalmic composition

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