EP2794828B1 - Composition de graisse - Google Patents

Composition de graisse Download PDF

Info

Publication number
EP2794828B1
EP2794828B1 EP12808414.2A EP12808414A EP2794828B1 EP 2794828 B1 EP2794828 B1 EP 2794828B1 EP 12808414 A EP12808414 A EP 12808414A EP 2794828 B1 EP2794828 B1 EP 2794828B1
Authority
EP
European Patent Office
Prior art keywords
meth
group
acrylate
grease
grease composition
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.)
Active
Application number
EP12808414.2A
Other languages
German (de)
English (en)
Other versions
EP2794828A1 (fr
Inventor
Yoshitomo Fujimaki
Keiji Tanaka
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 EP2794828A1 publication Critical patent/EP2794828A1/fr
Application granted granted Critical
Publication of EP2794828B1 publication Critical patent/EP2794828B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • 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
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2207/10—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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • 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
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • 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

  • the present invention relates to a grease composition and, more particularly, to a grease composition with high wear resistance.
  • the sliding parts and the rotating parts of machines require some kind of lubricating substrate and lubricating oils or greases are mostly employed therein with, in particular, very many machines utilizing a grease lubrication system where the sealing structure can be simplified and equipment made small and compact.
  • the range of use is extremely broad, encompassing, for example, the various kinds of ball-and-roller bearings and sliding bearings which support rotating bodies, and also the sliding parts of ball joints and links or chains, gear wheels, wires and booms of cranes, etc., and the quality demanded of these rises year by year, with the prolongation of machine life and maintenance-free operation being problems common to all machinery.
  • the cases where the lubricating performance of a grease in the rotating components or sliding parts of a machine falls, and the machine life runs out may be broadly divided into two. Firstly, there is the case where the grease is subject to oxidation when used at high temperature, so that there is solidification of the grease due to evaporation of the oil component or thermal polymerization, or the grease structure breaks down along with the formation of organic acids or aldehydes, resulting in lubrication failure.
  • Measures for overcoming the situation described in the first case above include methods aimed at extending the machine life by effectively incorporating a suitable antioxidant into the grease (see Japanese Patent 2085136 ), or using, as a grease ingredient, a thickener or a base oil which undergoes little structural or chemical change due to heat, thereby enhancing the function of the grease as a whole so that the machine life is prolonged.
  • Urea-based greases are one example of thermally stable thickeners and recently there have been many technical developments employing such thickeners (see Japanese Patent 4769456 ).
  • urea greases Since they have a higher dropping point than a grease employing a lithium soap as a thickener, and since they are outstanding in their heat stability and also in their wear resistance and lubricity, urea greases have come to be used in a wide range of fields. For example, in the automotive industry, the levels demanded for heat resistance, wear resistance and friction characteristics in regard to various kinds of motor vehicle components such as CVJs (constant velocity joints), electric power steering, alternator bearings and wheel bearings, etc., have been steadily increasing, so there are many cases where the outstanding performance and additive technology of the urea greases are being applied.
  • CVJs constant velocity joints
  • electric power steering alternator bearings and wheel bearings, etc.
  • the grease employed in motor vehicle components is designed and produced taking into account regular use under extremely cold conditions of about - 40°C and also at high temperatures of 100°C and above (radiant heat from the engine compartment + heat emitted from the road surface) so, as well as obtaining low stabilized torque characteristics over a wide temperature range from low to high temperatures, a grease is demanded which does not show deficient oiling due to a drop in viscosity at high temperatures and which also itself has a long life to match the life of the vehicle.
  • Measures for overcoming the situation described in the second case above include methods where the grease base oil viscosity is raised and polymer or other viscosity enhancing agent incorporated, so that the lubricating film is thickened and metal/metal contact suppressed (see JP-A-2008-69282 ), and methods where an antiwear agent, an extreme pressure agent, a solid lubricant or other load-resisting additive is incorporated into the grease so that, by the chemical or physical action of this additive, a coating or solid film is formed between the sliding faces and the surfaces thereby protected (see Japanese Patent 3833756 and JP-A-2-18497 ).
  • the structure of the grease may be altered, and there are also many additives which have an adverse effect on the machine components.
  • thiophosphates of high acid value have the disadvantage of readily reacting with the free alkali of a soap-based grease
  • olefin sulphide type additives may bring about hardening of a urea grease with the passage of time.
  • additives with strong chemical activity there are many issues such as discoloration or the corrosion of metals being caused and the strength of sealing materials like nitrile, acrylic or urethane rubbers being lowered.
  • US 3 130 161 A discloses a lubricating oil and anti-wear additives therefor.
  • the present invention addresses the problem of providing a grease composition with high wear resistance.
  • the present inventors have discovered that it is possible to raise the wear resistance of a grease by employing a poly(meth)acrylate derivative which contains hydroxyl groups and, in this way, it is possible to solve the aforesaid problem.
  • the present invention provides a grease composition which is characterized in that, in a grease composition containing a base oil and a thickener, there is employed, as an additive, a poly(meth)acrylate derivative containing hydroxyl groups.
  • the grease composition relating to the present invention displays the effect of higher wear resistance when compared to conventional grease compositions.
  • the grease composition of this embodiment contains, as indispensable constituent components, "base oil”, “thickener” and “additive”. Below, the individual components contained in the grease composition, the amounts (blended quantities) of the components in the grease composition, the method of producing the grease composition, the properties of the grease composition, and applications of the grease composition are explained in turn.
  • the base oil employed in the grease composition of this mode of the invention is not particularly restricted.
  • the mineral oils, synthetic oils, animal/vegetable oils, and mixtures thereof used in normal grease compositions.
  • the base oils belonging to Group I, Group II, Group III and Group IV, etc., of the API (American Petroleum Institute) base oil categories can be used on their own or in the form of mixtures.
  • the Group I base oils include paraffinic mineral oils obtained by, for example, applying a suitable combination of purification means such as solvent refining, hydro-refining and dewaxing, etc., to the lubricating oil fraction obtained by the atmospheric distillation of crude oil.
  • Group II base oils include paraffinic mineral oils obtained by, for example, applying a suitable combination of purification means such as hydro-cracking and dewaxing, etc., to the lubricating oil fraction obtained by the atmospheric distillation of crude oil.
  • the Group II base oils produced by a hydro-refining method such as the Gulf Co. method have a total sulphur component content of less than 10 ppm and an aromatics content of no more than 5%, and can be favourably employed in the present invention.
  • Group III base oils and Group II+ base oils include, for example, the paraffinic mineral oils produced by subjecting the lubricating oil fraction obtained by the atmospheric distillation of crude oil to high level hydro-refining, and also base oils refined by the Isodewaxing process where the wax formed in the dewaxing process is converted to isoparaffins, as well as the base oils produced by the Mobil Wax Isomerization process, and these too can be favourably used in this mode of the invention.
  • the synthetic oils include polyolefins, the diesters of dibasic acids like dioctyl sebacate, polyol esters, alkylbenzenes, alkylnaphthalenes, esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyl diphenyl ethers, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins and the like), and silicones, etc.
  • the aforesaid polyolefins include various types of olefin polymer and also their hydrogenated products.
  • any olefin may be used, and examples are ethylene, propylene, butene, and ⁇ -olefins with five or more carbon atoms.
  • a single type of aforesaid olefin may be used on its own, or a combination of two or more types may be employed.
  • the polyolefins referred to as poly- ⁇ -olefin (PAO) synthetic oils are preferred, and these are Group IV base oils.
  • oils obtained by a GTL (gas to liquid) process which are oils synthesized from natural gas in a liquid fuel conversion technique employing the Fischer Tropsch method, have an extremely low sulphur component and aromatic component content when compared to the mineral oil base oils obtained by the refining of crude oil, and the paraffin structure proportion is extremely high, with the result that they have outstanding oxidation stability and an extremely low evaporation loss, so these can be favourably employed as the base oil in the present mode of the invention.
  • the thickener used as an indispensable component in this mode of the invention are the compounds represented by general formula (I) : R 1 -NHCONH-R 2 -NHCONH-R 3 (I) (where R 1 and R 3 each represents a C 8-12 aliphatic hydrocarbon group, and R 2 represents a C 6-15 divalent aromatic group).
  • R 1 and R 3 are mutually independently an eight-carbon octyl group or a twelve-carbon lauryl group.
  • R 2 is preferably the diphenylmethane group.
  • R 2 is the diphenylmethane group and (1) R 1 and R 3 are eight-carbon octyl groups, or (2-1) a mixture of the compound where R 1 and R 3 are each eight-carbon octyl groups and the compound where R 1 and R 3 are twelve-carbon lauryl groups, (2-2) the compound where either R 1 or R 3 is the eight-carbon octyl group while the other from amongst R 1 and R 3 is the twelve-carbon lauryl group, and (2-3) a mixture of one or both of the compounds in (2-1) and the compound in (2-2).
  • (2-1) to (2-3) are particularly preferred.
  • the grease composition in this mode of the invention it is possible to jointly employ another thickener along with the main thickener ⁇ which is, for example, an aforesaid urea compound (such as an alkyl diurea) ⁇ .
  • a urea compound as the main thickener
  • tribasic calcium phosphate an alkali metal soap, an alkali metal complex soap, an alkaline earth metal soap, an alkaline earth complex soap, an alkali metal sulphonate, an alkaline earth metal sulphonate, other metal soaps, a metal terephthalamate salt, clay, a silica aerogel or other type of silica (silicon oxide), or a fluoropolymer such as polytetrafluoroethylene, etc., and one of these can be used on its own or two or more can be used in combination.
  • the additive employed as an indispensable component in this embodiment is a poly(meth)acrylate which contains hydroxyl groups.
  • This poly(meth)acrylate containing hydroxyl groups is a copolymer, and comprises a copolymer based on an alkyl (meth)acrylate having a C 1-20 alkyl group, and a hydroxyl-group-containing vinyl monomer, as the indispensable constituent monomers thereof.
  • the monomers belonging to (a1) and (a2) are preferred, with those belonging to (a2) further preferred.
  • those with 10 to 20 carbons in the alkyl group are preferred and those with 12 to 14 carbons are further preferred.
  • the aforesaid hydroxyl-group-containing vinyl monomer (b), from which the copolymer is composed along with the alkyl (meth)acrylate having a C1-20 alkyl group, is a vinyl monomer containing one or more (preferably 1 or 2) hydroxyl groups in the molecule. Specific examples are
  • copolymerized monomers are aliphatic hydrocarbon-type vinyl monomers (d).
  • examples of these are C 2-20 alkenes [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.] and C 4-12 alkadienes [butadiene, isoprene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, etc.].
  • alicyclic hydrocarbon-type vinyl monomers examples of which are cyclohexene, (di)cyclopentadiene, pinene, limonene, indene, vinylcyclohexene and ethylidene bicycloheptene, etc.
  • aromatic hydrocarbon-type vinyl monomers examples of which are styrene, ⁇ -methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, 4-crotylbenzene and 2-vinylnaphthalene, etc.
  • vinyl esters, vinyl ethers and vinyl ketones examples of which are the vinyl esters of saturated C 2-12 fatty acids [vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, etc.], C 1-12 alkyl, aryl or alkoxyalkyl vinyl ethers [methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl 2-methoxyethyl ether, vinyl 2-butoxyethyl ether, etc.] and C 1-8 alkyl or aryl vinyl ketones [methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, etc.].
  • esters of unsaturated polycarboxylic acids (h) examples of which are the alkyl, cycloalkyl and aralkyl esters of unsaturated polycarboxylic acids, in particular the c 1-8 alkyl diesters of unsaturated dicarboxylic acids [such as maleic acid, fumaric acid and itaconic acid] [like dimethyl maleate, dimethyl fumarate, diethyl maleate and dioctyl maleate, etc.].
  • vinyl monomers which contain a polyoxyalkylene chain (but not containing hydroxyl groups) (i): examples of these being the mono-(meth) acrylates of a mono-alkyl (C 1-18 ) ether of a polyoxyalkylene glycol (C 2-4 alkylene group; degree of polymerization 2-50) or of a polyoxyalkylene polyol [polyoxyalkylene ether of an aforesaid tri- to octa-hydric alcohol (C 2-4 alkyl group; degree of polymerization 2-100)], [such as methoxy polyethylene glycol (Mw 110-310) (meth)acrylate, or the (meth)acrylate of a lauryl alcohol ethylene oxide (2-30 mol) adduct, etc.]
  • carboxyl group-containing vinyl monomers (j) examples of which are vinyl monomers containing a single carboxyl group like unsaturated monocarboxylic acids [(meth)acrylic acid, ⁇ -methyl (meth) acrylic acid, crotonic acid, cinnamic acid, etc.] and the monoalkyl (C 1-8 ) esters of unsaturated dicarboxylic acids [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, etc.]; and vinyl monomers containing two or more carboxyl groups like maleic acid, fumaric acid, itaconic acid and citraconic acid, etc.
  • the monomers (c) are preferred, and two or more of these monomers (c) may be used in combination.
  • the monomers (c) are preferred, with dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate further preferred.
  • the hydroxyl value (hydroxyl group value) of the poly(meth)acrylate containing hydroxyl groups used as the additive lies between 10 and 100, preferably between 20 and 50, and more preferably between 25 and 35.
  • the hydroxyl value is a numerical value obtained by measurement based on JIS K3342 (1961), and it expresses the amount of hydroxyl groups in the additive.
  • a major difference between a lubricating oil and a grease is that, in the case of a grease, the thickener and additive forming the framework of the grease structure interact together and so, whereas an effect may be manifested in the case of a lubricating oil, with a grease there may be no effect at all, or, alternatively, wear may actually be promoted. Consequently, an additive which is stable and confers effective lubricity in terms of the grease is extremely favourable, as in the case of this present technique.
  • the grease composition of this mode of the invention may also optionally contain further additives such as antioxidants, rust inhibitors, oiliness agents, extreme pressure agents, anti-wear agents, solid lubricants, metal deactivators, polymers, metal-based cleaning agents, non metal-based cleaning agents, colouring agents, and the like.
  • antioxidants include 2,6-di- tert -butyl-4-methylphenol, 2,6-di- tert- butyl-p-cresol, p,p'-dioctyldiphenyl ⁇ amine, N-phenyl- ⁇ -naphthylamine and phenothiazine.
  • rust inhibitors examples include oxidized paraffin, carboxylic acid metal salts, sulphonic acid metal salts, carboxylic acid esters, sulphonic acid esters, salicylic acid esters, succinic acid esters, sorbitan esters and various kinds of amine salts.
  • oiliness agents, extreme pressure agents and anti-wear agents include zinc dialkyldithiophosphate sulphide, zinc diallyldithiophosphate sulphide, zinc dialkyldithiocarbamate sulphide, zinc diallyldithiocarbamate sulphide, molybdenum dialkyldithiophosphate sulphide, molybdenum diallyldithiophosphate sulphide, molybdenum dialkyldithiocarbamate sulphide, molybdenum diallyldithiocarbamate sulphide, organomolybdenum complexes, olefin sulphide, triphenyl phosphate, triphenyl-phosphorothionate, tricresyl phosphate and other phosphate esters, and sulphurized oil/fats, etc.
  • Examples of the solid lubricants include molybdenum disulphide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene), tungsten disulphide, graphite fluoride and calcium phosphate.
  • Examples of the metal deactivators include N,N'-disalicylidene-1,2-diaminopropane, benzotriazole, benzimidazole, benzothiazole and thiadiazole, etc.
  • Examples of the polymers include polybutene, polyisobutene, polyisobutylene, polyisoprene, polymethacrylate, and the like.
  • Examples of the metal-based cleaning agents are metal sulphonates, metal salicylates and metal phenates.
  • Examples of the non metal-based cleaning agents include succinimides and the like. However, these examples are not intended to restrict the invention.
  • the blended amount of base oil is preferably from 60-95 mass%, more preferably 70-90 mass% and still more preferably 75-90 mass%, taking the total grease composition as 100 mass%.
  • the amount of thickener incorporated is from 1-20 mass% , preferably 2-17 mass% and more preferably 3-15 mass%, taking the total grease composition as 100 mass%.
  • the amount of hydroxyl-group-containing poly(meth)acrylate incorporated is preferably from 2-20 mass% and more preferably 4-10 mass%, taking the total grease composition as 100 mass%.
  • the amount of the other additives is, for example, from 0.03 to 20 mass% by total of these optional components, taking the total grease composition as 100 mass%.
  • the grease composition of this mode of the invention can be produced by generally-used grease production methods and is not particularly restricted but, as an example of the method for producing a urea grease composition, a diurea thickener obtained by the reaction of 1 mol of diisocyanate and 2 mol of primary monoamine as the starting materials for the urea thickener, or a tetraurea grease thickener obtained by the reaction of 2 mol of diisocyanate and 1 mol of primary diamine plus 2 mol of primary monoamine as the starting materials for the urea thickener, or a triurea-monoureathane obtained by the reaction of 2 mol of diisocyanate, 1 mol of primary diamine, 1 mol of primary monoamine plus 1 mol of mono-alcohol as the starting materials for the urea thickener, is synthesized along with the base oil in each case in a grease production kettle, to produce the grease used.
  • a diurea thickener obtained by the reaction of 1 mol of diiso
  • the temperature is raised to a temperature of about 180°C, after which cooling is performed and, at a temperature of 100-80°C, the additive ⁇ the hydroxyl-group-containing poly(meth)acrylate derivative ⁇ is incorporated and thorough mixing performed, following which the mixture is cooled to room temperature. Thereafter, a homogenous grease composition can be obtained using a kneading machine (such as a triple roll mill or the like).
  • the dropping point of the grease composition in this mode of the invention is preferably at least 180°C, more preferably at least 210°C, still more preferably at least 250°C and in particular over or above 260°C. If the dropping point of the grease composition is at least 180°C, it is thought that the possibility of lubrication problems arising such as, for example, loss in viscosity at high temperature and accompanying leakage or seizing, etc., is suppressed.
  • the dropping point refers to the temperature at which there is breakdown of the thickener structure in the case of a grease possessing viscosity, when the temperature is raised. Measurement of the dropping point can be carried out in accordance with JIS K2220 8.
  • the consistency of the grease in this mode of the invention preferably lies between grade 000 and grade 6 (85-475), more preferably between grade 0 and grade 4 (175-385), and still more preferably between grade 1 and grade 3 (220-340).
  • the consistency denotes the physical hardness of the grease.
  • measurement of the worked penetration may be carried out in accordance with JIS K2220 7.
  • Friction testing was carried out based on the high speed four ball wear test in ASTM D2596, using steel ball bearings under conditions comprising a rotation rate of 1200 rpm, a load of 40 kgf and ambient temperature (no temperature control) for 30 minutes, and then evaluation conducted from the wear-scar diameter on the stationary balls.
  • the grease composition of this mode of the invention can be employed for generally-used machinery, bearings and gears, etc., but it can also show outstanding performance under more severe conditions, such as under high temperature conditions.
  • the starter, the alternator, various types of actuator unit and other engine peripherals the driveshaft, constant velocity joints (CVJs), wheel bearings, the clutch and other regions of the powertrain, the electric power steering (EPS), braking equipment, ball joints, door hinges, handles, the cooling fan motor, brake expanders and various other types of components, etc.
  • CVJs constant velocity joints
  • EPS electric power steering
  • braking equipment ball joints, door hinges, handles
  • the cooling fan motor brake expanders and various other types of components, etc.
  • the starting materials employed in the working examples and comparative examples were as follows.
  • thickeners A and B diurea components with the following chemical structures were employed as thickeners.
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 1 obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
  • 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • the octylamine and laurylamine were respectively dissolved in the remaining 40 wt% of the Group I base oil, and then introduced, in turn, into the trial-production kettle, to bring about reaction and formation of the diurea type II thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly(meth)acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 1 was obtained using a triple roll mill.
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 2 obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
  • 60 wt% of the total amount of the previously-prepared synthetic oil, i.e. base oil B was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • the octylamine was dissolved in the remaining 40 wt% of the synthetic oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type I thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly(meth)acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 2 was obtained using a triple roll mill.
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 3 obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
  • 60 wt% of the total amount of the previously-prepared Group III base oil, i.e. base oil C was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • the octylamine was dissolved in the remaining 40 wt% of the Group III base oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type I thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly(meth)acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 3 was obtained using a triple roll mill.
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the greases according to Working Examples 4 to 6 respectively obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for each of the diurea grease thickeners used here was a ratio of 1 : 2.
  • 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 7 obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
  • 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • the octylamine was dissolved in the remaining 40 wt% of the Group I base oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type I thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly(meth)acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 7 was obtained using a triple roll mill.
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 8 obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
  • the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • the octylamine was mixed with the synthetic oil, i.e. base oil B, and the laurylamine was mixed and dissolved in base oil C belonging to Group III, and these introduced in turn into the trial-production kettle, to bring about reaction and formation of the diurea type II thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly(meth)acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 8 was obtained using a triple roll mill.
  • additive A that is to say the hydroxyl-group-containing poly(meth)acrylate derivative
  • the starting materials, base oil and additive were prepared and measured out in the proportions shown in Table 1, and the grease according to Working Example 9 obtained by the usual method for producing a urea grease.
  • the mol ratio of the diisocyanate and primary amine which constituted the starting materials for the diurea grease thickener used here was a ratio of 1 : 2.
  • 60 wt% of the total amount of the previously-prepared Group I base oil, i.e. base oil A was introduced into a sealed grease trial-production kettle, immediately after which the diphenylmethane-4,4'-diisocyanate starting material for the urea thickener was added and, while stirring, the temperature raised to 50°C.
  • aniline was mixed and dissolved in the remaining 40 wt% of the Group I base oil, and introduced into the trial-production kettle, to bring about reaction and formation of the diurea type III thickener. Heating was then continued and the temperature raised to about 180°C, to bring about stabilization of the thickener structure. Subsequently, cooling was commenced and, at a temperature of 80°C during the cooling process, additive A, that is to say the hydroxyl-group-containing poly(meth)acrylate derivative, was added, and, after thorough stirring and mixing, cooling was continued down to room temperature. Thereafter, the homogeneous grease of Working Example 9 was obtained using a triple roll mill.
  • Comparative Example 1 was the base grease in which no additive was incorporated.
  • Comparative Example 2 additive B was incorporated.
  • Comparative Example 3 additive C was incorporated.

Landscapes

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

Claims (7)

  1. Une composition de graisse comprenant une huile de base, un épaississant et un poly(méth)acrylate qui contient des groupes hydroxyles, dans laquelle l'épaississant est un composé urée formé par la réaction entre un isocyanate et une amine primaire ;
    dans laquelle le composé urée est un composé représenté par la formule générale (I) :

            R1-NHCONH-R2-NHCONH-R3     (I)

    dans laquelle R1 et R3 représentent chacun un groupe hydrocarboné aliphatique en C8 à C12, et R2 représente un groupe aromatique divalent en C6 à C15 ; et
    dans laquelle l'épaississant est présent en une quantité de 1 à 20 % en masse, amenant la composition totale de graisse à 100 % en masse.
  2. Composition de graisse selon la revendication 1, dans laquelle le poly(méth)acrylate qui contient des groupes hydroxyles est un copolymère ayant comme monomères constitutifs un (méth)acrylate d'alkyle ayant un groupe alkyle en C1 à C20, et un monomère vinylique contenant un groupe hydroxyle.
  3. Composition de graisse selon la revendication 2, dans laquelle le (méth)acrylate d'alkyle ayant un groupe alkyle en C1 à C20 est un (méth)acrylate d'alkyle ayant un groupe alkyle en C8 à C20.
  4. Composition de graisse selon la revendication 2 ou la revendication 3, dans laquelle le monomère vinylique contenant un groupe hydroxyle est choisi parmi les (méth)acrylates d'hydroxyalkyle (C2 à C6), les (méth)acrylamides mono- ou di-hydroxyalkyle (C1 à C4)-substitués, l'alcool vinylique formé par l'hydrolyse de motifs d'acétate de vinyle, les alcénols C3 à C12, les alcènes diols C4 à C12, l'hydroxyalkyle (C1 à C6) les éthers d'alcényle (C3 à C10), les monomères aromatiques contenant un groupe hydroxyle, les polyols et les monomères vinyliques contenant une chaîne polyoxyalkylène et un ou des groupes hydroxyle(s).
  5. Composition de graisse selon l'une quelconque des revendications 2 à 3, dans laquelle le copolymère a d'autres monomères constitutifs choisis parmi les monomères contenant des groupes nitro, les monomères vinyliques contenant des groupes amino primaires, secondaires ou tertiaires, les monomères vinyliques amphotères et les monomères contenant un groupe nitrile.
  6. Composition de graisse selon l'une quelconque des revendications précédentes, dans laquelle l'indice d'hydroxyle du poly(méth)acrylate contenant des groupes hydroxyles est de 20 à 50, mesuré selon la norme JIS K3342 (1961).
  7. Composition de graisse selon l'une quelconque des revendications précédentes, comprenant de 60 à 95 % en masse d'huile de base, et de 2 à 20 % en masse du poly(méth)acrylate qui contient des groupes hydroxyles, amenant la composition de graisse totale à 100 % en masse.
EP12808414.2A 2011-12-22 2012-12-21 Composition de graisse Active EP2794828B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011281987A JP5826626B2 (ja) 2011-12-22 2011-12-22 グリース組成物
PCT/EP2012/076851 WO2013093104A1 (fr) 2011-12-22 2012-12-21 Composition de graisse

Publications (2)

Publication Number Publication Date
EP2794828A1 EP2794828A1 (fr) 2014-10-29
EP2794828B1 true EP2794828B1 (fr) 2019-09-04

Family

ID=47458998

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12808414.2A Active EP2794828B1 (fr) 2011-12-22 2012-12-21 Composition de graisse

Country Status (9)

Country Link
US (1) US20150045272A1 (fr)
EP (1) EP2794828B1 (fr)
JP (1) JP5826626B2 (fr)
KR (1) KR20140107557A (fr)
CN (1) CN104011190A (fr)
BR (1) BR112014015186A2 (fr)
IN (1) IN2014CN04606A (fr)
RU (1) RU2628512C2 (fr)
WO (1) WO2013093104A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6754565B2 (ja) * 2015-01-21 2020-09-16 セイコーインスツル株式会社 グリース、転がり軸受、転がり軸受装置及び情報記録再生装置
JP6316900B2 (ja) * 2015-11-10 2018-04-25 ミネベアミツミ株式会社 グリース組成物、転がり軸受、およびモータ
US20180371352A1 (en) * 2015-11-24 2018-12-27 Shell Oil Company Method for improving the air release of a lubricating oil
JP6841595B2 (ja) * 2015-12-25 2021-03-10 協同油脂株式会社 減速機用潤滑剤組成物及び減速機
DE112017003959B4 (de) * 2016-08-08 2024-01-18 Nok Klueber Co., Ltd. Schmierfettzusammensetzung und deren Verwendung
JP6919848B2 (ja) 2017-05-01 2021-08-18 出光興産株式会社 グリース組成物
US11078438B2 (en) * 2017-07-24 2021-08-03 Chemtool Incorporated Extreme pressure metal sulfonate grease
BR112020021795A2 (pt) * 2018-04-26 2021-02-17 Shell Internationale Research Maatschappij B.V. composição lubrificante e uso da mesma como veda-juntas
JP6755905B2 (ja) * 2018-07-27 2020-09-16 ミネベアミツミ株式会社 樹脂潤滑用グリース組成物および樹脂摺動部材
CN109913287B (zh) * 2019-03-28 2022-05-20 中国石油化工股份有限公司 一种四脲润滑脂及制备方法
CN111040846A (zh) * 2019-12-09 2020-04-21 安徽中天石化股份有限公司 一种环境友好型长寿命润滑脂及其生产工艺
CN111394150B (zh) * 2020-04-23 2022-01-28 沈阳理工大学 一种耐高温五聚脲润滑脂及其制备方法
JP7455376B2 (ja) 2020-06-29 2024-03-26 株式会社ニッペコ グリース組成物
WO2022107882A1 (fr) * 2020-11-20 2022-05-27 日本精工株式会社 Composition de graisse et dispositif à roulement
CN112795418A (zh) * 2020-12-08 2021-05-14 青岛中科润美润滑材料技术有限公司 一种芳香类二胺制备四脲润滑脂组合物及其制备方法
CN112591733B (zh) * 2020-12-16 2022-07-12 正大国际科技(常德)集团有限公司 改性的气凝胶纳米颗粒及其应用
CN113372978A (zh) * 2021-05-28 2021-09-10 中国石油化工股份有限公司 一种高温食品机械润滑脂组合物及其制备方法与应用
WO2023199911A1 (fr) * 2022-04-11 2023-10-19 協同油脂株式会社 Composition de graisse

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006069986A1 (fr) * 2004-12-27 2006-07-06 Shell Internationale Research Maatschappij B.V. Composition de graisse lubrifiante à base d'urée

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE584708A (fr) * 1958-11-18
US3354086A (en) * 1964-05-28 1967-11-21 Exxon Research Engineering Co Grease lubricant
US4842660A (en) 1986-03-28 1989-06-27 New Jersey Machine, Inc. Continuous motion pressure sensitive labeling system and method
JPH0218497A (ja) 1988-07-07 1990-01-22 Kyodo Yushi Kk 耐高荷重グリース組成物
JP3833756B2 (ja) 1996-10-18 2006-10-18 昭和シェル石油株式会社 ウレアグリース組成物
DE10080471T1 (de) * 1999-02-12 2001-04-26 Nsk Ltd Rollenvorrichtung
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
US7579305B2 (en) * 2002-03-27 2009-08-25 Sanyo Chemical Industries, Ltd. Friction regulator for lubricating oil and lubricating oil composition
US7429555B2 (en) * 2004-04-30 2008-09-30 Rohmax Additives Gmbh Lubricating grease with high water resistance
JP2006077119A (ja) 2004-09-09 2006-03-23 Nok Kluber Kk 潤滑油組成物
JP2008069282A (ja) 2006-09-14 2008-03-27 Ntn Corp 等速ジョイント用グリース組成物および等速ジョイント
JP4976795B2 (ja) * 2006-09-21 2012-07-18 昭和シェル石油株式会社 ウレアグリース組成物
CN101535455A (zh) * 2006-11-01 2009-09-16 昭和砚壳石油株式会社 包含具有羟基的聚(甲基)丙烯酸酯和二硫代磷酸金属盐的润滑油组合物
US20100105585A1 (en) * 2008-10-28 2010-04-29 Carey James T Low sulfur and ashless formulations for high performance industrial oils
JP5455480B2 (ja) * 2009-07-15 2014-03-26 昭和シェル石油株式会社 潤滑油組成物
CN102002414A (zh) * 2010-10-13 2011-04-06 中国石油化工股份有限公司 一种聚脲润滑脂组合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006069986A1 (fr) * 2004-12-27 2006-07-06 Shell Internationale Research Maatschappij B.V. Composition de graisse lubrifiante à base d'urée
JP4769456B2 (ja) * 2004-12-27 2011-09-07 昭和シェル石油株式会社 ウレア系潤滑グリース組成物、転がり軸受けおよび電動パワーステアリング装置

Also Published As

Publication number Publication date
KR20140107557A (ko) 2014-09-04
JP2013129794A (ja) 2013-07-04
WO2013093104A1 (fr) 2013-06-27
EP2794828A1 (fr) 2014-10-29
RU2014130103A (ru) 2016-02-20
IN2014CN04606A (fr) 2015-09-18
CN104011190A (zh) 2014-08-27
US20150045272A1 (en) 2015-02-12
RU2628512C2 (ru) 2017-08-17
JP5826626B2 (ja) 2015-12-02
BR112014015186A2 (pt) 2017-06-13

Similar Documents

Publication Publication Date Title
EP2794828B1 (fr) Composition de graisse
EP2785821B1 (fr) Composition de graisse
EP2935539B1 (fr) Composition de graisse
JP5646859B2 (ja) 無段変速機用潤滑油組成物
EP2687584B1 (fr) Composition de graisse
CN109477018B (zh) 混合润滑脂
US11220650B2 (en) Grease composition
US20210171858A1 (en) Grease composition
JP2024051125A (ja) グリース組成物
EP2631284B1 (fr) Composition de graisse
JP6703849B2 (ja) プロペラシャフトスプライン用グリース組成物およびプロペラシャフトスプライン
EP3548589B1 (fr) Composition de graisse
JP5620080B2 (ja) グリース組成物の耐荷重性向上剤及び向上方法
EP3178910B1 (fr) Composition de graisse
KR20210107689A (ko) 볼 조인트용 윤활제 조성물
JP5486246B2 (ja) 潤滑剤組成物
JP2023093885A (ja) ウレアグリース組成物
WO2023182532A1 (fr) Composition de graisse
JP2023128103A (ja) グリース組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140630

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180725

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190517

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1175350

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190915

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012063696

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190904

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191205

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1175350

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200106

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200224

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012063696

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG2D Information on lapse in contracting state deleted

Ref country code: IS

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200105

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20200605

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20191221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191221

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191221

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20121221

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190904

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230425

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231024

Year of fee payment: 12