EP2935539B1 - Schmierfettzusammensetzung - Google Patents

Schmierfettzusammensetzung Download PDF

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Publication number
EP2935539B1
EP2935539B1 EP13811953.2A EP13811953A EP2935539B1 EP 2935539 B1 EP2935539 B1 EP 2935539B1 EP 13811953 A EP13811953 A EP 13811953A EP 2935539 B1 EP2935539 B1 EP 2935539B1
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EP
European Patent Office
Prior art keywords
acid
grease
mass
fatty acid
lithium
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EP13811953.2A
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English (en)
French (fr)
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EP2935539A1 (de
Inventor
Kazuya Watanabe
Keiji Tanaka
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/02—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a non-macromolecular 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2205/028—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
    • 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
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • C10M2207/1225—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
    • C10M2207/1415—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the present invention relates to a grease composition. More specifically, the present invention relates to a heat-stable lithium-containing calcium complex-based grease composition which has a high dropping point and excellent shear stability, and exhibits long bearing life.
  • JP-A-2006-131721 proposes lithium complex grease comprising a lithium salt of an aliphatic monocarboxylic acid, a lithium salt of an aromatic dibasic acid and a lithium salt of an aliphatic dibasic acid, which is a grease that has a better higher dropping point than lithium grease and allows a wider temperature range for use.
  • lithium which is the starting material of lithium grease, is not limited in its use to grease and is variously used in other fields, there is concern about resource depletion or a steep rise in cost in the future due to a recent increase in demand.
  • lithium complex grease has problems in that the production procedure is complex and a longer time is required because the reaction of two kinds of aliphatic acid comprises two stages.
  • EP2154229A2 concerns a calcium/lithium complex composition
  • a calcium/lithium complex composition comprising (a) at least a base oil, (b) at least one additive, (c) at least comprising a thickener, wherein the thickener is a complex soap, a calcium/lithium soap and at least one complexing agent and (d) Ca(OH) 2 , said composition having a calcium to lithium molar ratio of greater than 1.0 to 5.0 to 1, based on the ratio of all the calcium and lithium atoms present in the calcium and lithium compounds.
  • JP-A-2008-231310 proposes diurea grease which can be used for a long period of time at a high temperature.
  • an amine compound such as aniline which is used as the starting material, is extremely toxic, extra care should be taken when handling for production, and therefore there is a safety problem.
  • grease compositions using lithium soap or urea as a thickener which are not quite satisfactory from the viewpoints of safety and burdens on the environment
  • grease compositions using calcium as a thickener have been investigated which have an advantage in terms of production cost in addition to safety and burden on the environment.
  • greases using calcium soap as a thickener usually have a poorer dropping point and thermal resistance than lithium grease, lithium complex grease or urea grease, and therefore greases using calcium soap do not meet requirements as grease suitable for current operating conditions.
  • JP-A-2009-249419 proposes a calcium complex grease having a high dropping point which uses as a thickener calcium soap comprising calcium salts of a dibasic acid and fatty acid.
  • a suitable consistency cannot be maintained if the added amount of thickener is small, and there is a restriction in the form of dibasic acid, especially terephthalic acid, which is used as a starting material, and the terephthalic acid has to be introduced at a high temperature of 120°C for production.
  • an objective of the present invention is to provide a heat-stable grease composition which comprises a grease that has a thermal resistance equivalent to or higher than greases using lithium soap or urea as a thickener, and has a high dropping point and excellent shear stability, and exhibits long bearing life.
  • the present invention provides a grease composition
  • a grease composition comprising base oil and, as thickener, calcium complex soap and lithium soap
  • the grease composition being characterised in that a C18-22 straight-chain, substituted or unsubstituted higher fatty acid, a substituted or unsubstituted aromatic monocarboxylic acid having a benzene ring and a C2-4 straight-chain saturated lower fatty acid are used as carboxylic acids constituting the calcium complex soap and lithium soap
  • carboxylic acids constituting the calcium complex soap and lithium soap
  • the mass ratio (Li/Ca) of the lithium metal content to the calcium metal content in the thickener starting material is 1 part per 100 to 5 parts per 100.
  • the grease composition may include a straight-chain higher fatty acid which is at least one selected from stearic acid, oleic acid, 12-hydroxystearic acid and behenic acid, an aromatic monocarboxylic acid which is at least one selected from benzoic acid and p-toluic acid, and a straight-chain saturated lower fatty acid which is at least one selected from acetic acid and butyric acid.
  • the method for producing the grease composition according to the present invention may be a method comprising the step of forming lithium-containing calcium complex soap by adding a straight-chain higher fatty acid, an aromatic monocarboxylic acid, a straight-chain saturated lower fatty acid, calcium hydroxide and lithium hydroxide to base oil.
  • the lithium-containing calcium complex grease composition according to the present invention has a high dropping point and maintains a suitable consistency, and in addition to the fact that the composition can be used under a high temperature environment, which was only possible with lithium-based grease or urea grease in the past, the composition exhibits safety, environmental and low-cost effects. Furthermore, the lithium-containing calcium complex grease composition according to the present invention has excellent shear stability, and exhibits thermal stability and long bearing life.
  • the grease composition of the present embodiment includes "base oil” and “thickener” as essential structural components.
  • components included in the grease composition the amount (blended amount) of each component in the grease composition, the method for producing the grease composition, the properties of the grease composition and the use of the grease composition will be described in said order.
  • the base oil for use in the grease composition of the present embodiment is not particularly restricted.
  • oil used in general grease compositions such as mineral oil, synthetic oil, animal and vegetable oils or mixed oil thereof may be appropriately selected.
  • base oils belonging to Group 1, Group 2, Group 3, Group 4 and the like in the API (American Petroleum Institute) base oil category may be used singly or as a mixture.
  • Examples of the Group 1 base oil include paraffin-based mineral oils which can be obtained by refining a lubricating oil distillate obtained from an atmospheric distillation of crude oil, by appropriately combining means of solvent refining, hydrotreating, dewaxing or the like.
  • Examples of the Group 2 base oil include paraffin-based mineral oils which can be obtained by refining a lubricating oil distillate obtained from an atmospheric distillation of crude oil, by appropriately combining means of hydrotreating, dewaxing or the like.
  • the Group 2 base oil refined by Gulf's hydrotreating or the like has less than 10 ppm sulphur content and at most 5% aroma content, and may be preferably used in the present invention.
  • Group 3 base oil and Group 2 plus base oil examples include paraffin-based mineral oils which can be manufactured by subjecting a lubricating oil distillate obtained from an atmospheric distillation of crude oil to high hydrogenation refinement, base oils refined by the ISODEWAX process according to which a wax produced by a dewaxing process is converted/dewaxed to isoparaffin, and base oils refined by the Mobil wax isomerisation process, and these oils may also be preferably used in the present embodiment.
  • Examples of synthetic oil include polyolefins, diesters of dibasic acid such as dioctyl sebacate, polyol esters, alkyl benzenes, alkyl naphthalenes, esters, polyoxyalkylene glycols, polyoxyalkylene glycol esters, polyoxyalkylene glycol ethers, polyphenyl ethers, dialkyl diphenyl ethers, fluorine-containing compounds (perfluoropolyether, fluorinated polyolefin and the like), silicones and the like.
  • the above-mentioned polyolefins include various olefin polymers and hydrogenated products thereof.
  • Any olefins may be used, and examples include ethylene, propylene, butene, ⁇ -olefins having 5 or more carbon atoms and the like.
  • Polyolefins may be produced by using one of the above-mentioned olefins or two or more of them in combination.
  • so-called poly- ⁇ -olefin (PAO) is preferably used as a polyolefin, which is a Group 4 base oil.
  • Oils synthesised by means of GTL (gas to liquid) by the Fischer-Tropsch process which is the technology of obtaining liquid fuel from natural gas, have significantly lower sulphur and aroma contents and a significantly higher paraffin component ratio than mineral base oils obtained by refining crude oils, and therefore exhibit excellent oxidation stability and extremely small evaporative loss.
  • the oils can be preferably used as the base oil of the present embodiment.
  • a thickener used in the present embodiment is lithium-containing calcium complex soap obtained by a plurality of carboxylic acids being reacted with a specific base (typical examples are calcium hydroxide and lithium hydroxide).
  • the term "complex" in the lithium-containing calcium complex soap according to the present embodiment means that a plurality of carboxylic acids are employed.
  • carboxylic acids for the lithium-containing calcium complex soap according to the present embodiment which are (1) higher fatty acid, (2) aromatic monocarboxylic acid and (3) lower fatty acid.
  • carboxylic acid moieties (anion moieties) in the lithium-containing calcium complex soap will be described.
  • stearic acid or behenic acid as the straight-chain higher fatty acid
  • benzoic acid or p-toluic acid as the aromatic monocarboxylic acid
  • acetic acid or butyric acid as the lower fatty acid
  • another thickener may also be used in combination with the above-mentioned lithium-containing calcium complex soap.
  • other thickeners include tricalcium phosphates, alkali metal soaps, alkali metal complex soaps, alkaline earth metal soaps, alkaline earth metal complex soaps (other than calcium complex soaps), alkali metal sulfonates, alkaline earth metal sulfonates, other metal soaps, terephthalamate metal salts, triurea monourethane, diurea, tetra-urea, other polyurea, clay, silica (silicon oxide) such as silica aerogel, or fluorine resins such as polytetrafluoroethylene, and the like. These may be used alone or in combination of two or more kinds.
  • any substances capable of imparting thickening effects to a liquid substance may be used.
  • the grease composition of the present embodiment may also include optional additives such as an antioxidant, an anti-rust agent, an oiliness improver, an extreme pressure additive, an anti-wear agent, a solid lubricant, a metal deactivator, a polymer, a metal-based cleaner, a non-metallic cleaner, a colouring agent and a water repellent agent, where the total amount of optional components is about 0.1 to 20 parts by mass based on 100 parts by mass of the total grease composition.
  • optional additives such as an antioxidant, an anti-rust agent, an oiliness improver, an extreme pressure additive, an anti-wear agent, a solid lubricant, a metal deactivator, a polymer, a metal-based cleaner, a non-metallic cleaner, a colouring agent and a water repellent agent, where the total amount of optional components is about 0.1 to 20 parts by mass based on 100 parts by mass of the total grease composition.
  • antioxidants examples include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-para-cresol, p,p'-dioctyldiphenylamine, N-phenyl- ⁇ -naphthylamine, phenothiazine and the like.
  • anti-rust agent examples include paraffin oxide, a metal salt of carboxylic acids, carboxylic acid ester, sulphonic acid ester, salicylic acid ester, succinic acid ester, sorbitan ester and other various amine salts.
  • Examples of an oiliness improver, extreme pressure additive and anti-wear agent include sulphurised zinc dialkyl dithiophosphate, sulphurised zinc diallyl dithiophosphate, sulphurised zinc dialkyl dithiocarbamate, sulphurised zinc diallyl dithiocarbamate, sulphurised molybdenum dialkyl dithiophosphate, sulphurised molybdenum diallyl dithiophosphate, sulphurised molybdenum dialkyl dithiocarbamate, sulphurised molybdenum diallyl dithiocarbamate, an organic molybdenum complex, a sulphurised olefin, triphenyl phosphate, triphenyl phosphorothionate, tricresine phosphate, other phosphate esters, sulphurised fats and oils and the like.
  • Examples of a solid lubricant include molybdenum disulphide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene), tungsten disulphide, graphite fluoride and the like.
  • Examples of a metal deactivator include N,N'-disalicylidene-1,2-diaminopropane, benzotriazole, benzimidazole, benzothiazole, thiadiazole and the like.
  • Examples of a polymer include polybutene, polyisobutene, polyisobutylene, polyisoprene, polymethacrylate and the like.
  • Examples of a metal-based cleaner include metal sulphonate, metal salicylate, metal phenate and the like.
  • Examples of a non-metallic cleaner include succinic acid imide and the like.
  • the blended amount of base oil is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, even more preferably 70 to 85 parts by mass, with respect to 100 parts by mass of the total grease composition.
  • the lithium-containing calcium complex soap as the thickener may be blended in an amount of preferably 1 to 40 parts by mass, more preferably 3 to 25 parts by mass, even more preferably 5 to 20 parts by mass, particularly preferably 15 to 20 parts by mass in terms of a starting material base, with respect to 100 parts by mass of the total grease composition.
  • the higher fatty acid in the lithium-containing calcium complex soap is blended in an amount of 3 to 25 parts by mass, with respect to 100 parts by mass of the entire grease composition.
  • the higher fatty acid in the lithium-containing calcium complex soap may be blended in an amount of 5 to 20 parts by mass with respect to 100 parts by mass of the entire grease composition.
  • the aromatic monocarboxylic acid in the lithium-containing calcium complex soap is blended in an amount of 0.5 to 3 parts by mass, with respect to 100 parts by mass of the total grease composition.
  • the aromatic monocarboxylic acid in the lithium-containing calcium complex soap may be blended in an amount of 0.75 to 2.5 parts by mass with respect to 100 parts by mass of the total grease composition.
  • the lower fatty acid in the lithium-containing calcium complex soap is blended in an amount of 1 to 5 parts by mass, with respect to 100 parts by mass of the total grease composition.
  • the lower fatty acid in the lithium-containing calcium complex soap may be blended in an amount of 2 to 4 parts by mass with respect to 100 parts by mass of the total grease composition.
  • the calcium content in the lithium-containing calcium complex soap is 3 to 15 parts by mass, more preferably 5 to 14 parts by mass, even more preferably 8 to 12 parts by mass, with respect to 100 parts by mass of the total thickener starting materials.
  • the lithium content in the lithium-containing calcium complex soap is 0.05 to 1 parts by mass, more preferably 0.1 to 0.6 parts by mass, even more preferably 0.15 to 0.5 parts by mass, with respect to 100 parts by mass of the total thickener starting materials.
  • the mass ratio of the lithium-containing calcium complex soap to the base oil is preferably about 99:1 to 60:40, more preferably about 95:5 to 65:35, even more preferably about 90:10 to 70:30.
  • the mass ratio of the higher fatty acid to the total carboxylic acid amount is preferably about 50 to 90%, more preferably about 60 to 80%, even more preferably about 65 to 75%.
  • the mass ratio of the aromatic monocarboxylic acid to the total carboxylic acid amount is preferably about 1 to 30%, more preferably about 3 to 20%, even more preferably about 5 to 15%. It is thought that with an aromatic monocarboxylic acid ratio of greater than 30%, a grease form cannot be obtained, and with a ratio of less than 1%, thermal resistance cannot be provided.
  • the mass ratio of the lower fatty acid to the total carboxylic acid amount is preferably about 7 to 35%, more preferably about 10 to 30%, even more preferably about 15 to 25%. It is thought that with a lower fatty acid ratio of greater than 35%, a grease form cannot be obtained, and with a ratio of less than 7%, thermal resistance cannot be provided.
  • the mass ratio of the aromatic monocarboxylic acid to the higher fatty acid is preferably about 3:97 to 30:70, more preferably about 5:95 to 25:75, even more preferably about 7:93 to 16:84. It is thought that when the aromatic monocarboxylic acid ratio based on the sum amount of higher fatty acid and aromatic monocarboxylic acid is greater than 30%, a grease form cannot be obtained, and when the ratio is less than 3%, thermal resistance cannot be provided.
  • the mass ratio of the higher fatty acid to the lower fatty acid is preferably about 85:15 to 65:35, more preferably about 83:17 to 70:30, even more preferably about 81:19 to 76:24. It is thought that when the lower fatty acid ratio based on the sum amount of higher fatty acid and lower fatty acid is greater than 35%, a grease form cannot be obtained, and when the ratio is less than 15%, thermal resistance cannot be provided.
  • the mass ratio of the lower fatty acid to the aromatic monocarboxylic acid is preferably about 55:45 to 15:85, more preferably about 50:50 to 20:80, even more preferably about 45:55 to 23:77. It is thought that when the lower fatty acid ratio based on the sum amount of aromatic monocarboxylic acid and lower fatty acid is greater than 90 mass%, a weak thickening effect is produced and a grease form cannot be obtained.
  • the mass ratio (Li/Ca) of the lithium metal content to the calcium metal content in the thickening agent starting material is 1 part per 100 to 5 parts per 100.
  • the numerical value is less than 0.3 parts per 100, there is no improvement in thermal resistance or shear stability, and extension of bearing life at high temperature cannot be expected, so is not preferable.
  • the numerical value is greater than 10 parts per 100, the grease softens and the feeling of body is lost, and then poor rolling stability (shear stability) is produced; it is therefore not preferable.
  • the grease composition of the present embodiment may be produced according to a method generally used for producing grease.
  • the production method is not particularly limited, and an example includes a method which involves mixing base oil, a higher fatty acid, a lower fatty acid and an aromatic monocarboxylic acid in a grease manufacturing vessel, and dissolving the contents at a temperature between 60 and 120°C.
  • calcium hydroxide and lithium hydroxide which are preliminarily dissolved and dispersed in an appropriate amount of distilled water are charged into the vessel.
  • a composition having a dropping point equal to or higher than 180°C is preferably used, a composition having a dropping point equal to or higher than 220°C is more preferably used, and a composition having a dropping point equal to or higher than 260°C is particularly preferably used.
  • the dropping point herein refers to the temperature at which viscous grease loses the thickener configuration with increase in temperature.
  • the dropping point is measured according to JIS K 2220 8.
  • the consistency of the grease of the present embodiment is preferably Nos. 1 to 4 (175 to 340), more preferably Nos. 2 to 3 (220 to 295) according to the consistency test.
  • the consistency indicates the apparent grease hardness.
  • the consistency is measured by carrying out worked penetration measurements according to JIS K 2220 7.
  • the grease composition of the present embodiment preferably shows an evaporation loss of less than 5% based on the thin film oven test (at 150°C for 24 hours).
  • the thin film oven test method is described as follows. That is, 3.0 g +/- 0.1 g of a sample is applied to the central area portion (50 mm ⁇ 70 mm) on one side of the test piece which is the SPCC steel sheet described in the humidity cabinet test according to JIS K 2246 which has dimensions of 1.0 mm thickness ⁇ 60 mm length ⁇ 80 mm width, the heat test is carried out at 150°C for 24 hours, the weight of the SPCC steel sheet before and after the heat test is respectively measured, and the evaporation amount is determined using the formula shown below.
  • the oxygen pressure loss due to an oxidation reaction according to an oxidation stability test is preferably 40 kPa or less, more preferably 30 kPa, and even more preferably 20 kPa or less.
  • the oxidation stability of grease refers to the resistance to oxidation of grease caused by a reaction with oxygen in air.
  • the grease composition deterioration due to oxidation has an influence on base oil, and in particular, has a great influence on oxidative decomposition of a thickener.
  • the basic function of a thickener is to hold the base oil and maintain the physical hardness of the grease in order to allow the base oil to stay on the lubrication part of a machine, and at the same time, the thickener plays a role in appropriately supplying the base oil component held by the thickener to sliding faces.
  • this thickener is destroyed by oxidation, the hardness originally possessed by the grease cannot be maintained and the ability to hold the base oil is lost, which base oil then slides off the lubrication part, and a suitable lubrication status cannot be maintained. This occurrence is greatly influenced by usage environment, and in particular, oxidative degradation accelerates with the increase in temperature.
  • the oxidation stability of the grease composition is extremely important in order for the lubrication part to maintain a suitable lubrication status and to improve the lubrication life.
  • the oxidation stability is measured according to JIS2220 12.
  • the grease consistency of the grease composition of the present embodiment after the rolling stability test is preferably 340 or less, more preferably 330 or less, even more preferably 320 or less.
  • the rolling stability test is used to evaluate the shear stability of the grease by measuring the consistency (hardness) of the grease after kneading 50 g of test grease with the device for a predetermined period of time.
  • the shear stability of the grease composition is an important element for maintaining the lubrication ability and physical behaviour of the grease. Poor shear stability causes grease to readily escape from the lubrication part of machine, and the required lubrication cannot be provided, which results in shortening of life, and also scattering of grease may occur which pollutes the surrounding area of the machine and impairs the working environment.
  • the rolling stability test which is used to evaluate the shear stability is carried out according to ASTMD 1831.
  • the life according to a grease bearing life test is preferably 200 hours or longer, more preferably 300 hours or longer, even more preferably 400 hours or longer.
  • 6.0 g of test grease is provided to a 6306 deep-groove radial ball bearing and the test grease-placed bearing is operated with a cycle of 20 hours operation and 4 hours rest at a temperature of 150°C.
  • the device has a mechanism wherein it stops when the power current of the motor that drives the bearing exceeds a certain level due to the subsequent loss of lubrication function of the grease and the consequent occurrence of poor bearing rotation. The time at which the device stops is read and recorded as the life of the grease.
  • the lubrication life of grease has a great impact on the physical behaviour of grease and on chemical deterioration, and loss in either function has a great impact on the lubrication life. For example, when grease turns into a liquid at high temperature or softens a lot due to shear in the bearing, grease escapes and is lost from the bearing and the lubricating oil supplementation is not achieved, which then results in shortening of life.
  • the grease composition of the present embodiment can, of course, be used for generally used machines, bearings, gears and the like, and exhibits excellent performance under severe conditions, for example, under high temperature conditions.
  • the grease composition may be preferably used for lubrication of various components in automobiles such as engine peripherals including the starter, alternator and various actuators, the powertrain including the propeller shaft, constant velocity joint (CVJ), wheel bearing and clutch, the electric power steering (EPS), brake unit, ball joint, door hinge, steering wheel, cooling fan motor, brake expander and the like.
  • the grease composition may also be preferably used in various high temperature/heavy duty parts in construction machinery such as a power shovel, bulldozer and crane truck, the steel industry, the papermaking industry, forestry machines, agricultural machines, chemical plants, power-generating facilities, drying furnaces, copying machines, railway vehicles, screw joints of seamless pipes and the like.
  • construction machinery such as a power shovel, bulldozer and crane truck
  • the steel industry the papermaking industry
  • forestry machines agricultural machines, chemical plants, power-generating facilities, drying furnaces, copying machines, railway vehicles, screw joints of seamless pipes and the like.
  • the composition may also be preferably used for hard disk bearings, plastic lubrication, cartridge grease and the like.
  • the starting materials used in the present Examples and Comparative examples are as follows. Unless otherwise particularly mentioned, the quantities shown in Table 1A were used for Examples 1 to 6 and in Table 1B for Comparative Examples 1 to 4.
  • the amount of starting materials shown in Table 1 ⁇ in particular, calcium hydroxide, lithium hydroxide and various carboxylic acids (higher fatty acid, aromatic monocarboxylic acid and lower fatty acid) ⁇ is the amount of reagent. Therefore, the actual component amount in the composition can be calculated on the basis of the numerical values in Tables 1A and 1B and the purity described below.
  • the commercially available all-purpose grease manufactured by Showa Shell Sekiyu K.K. was used.
  • the thickener was lithium 12-hydroxystearate soap, and the base oil was mineral oil-based lubricating oil.
  • the viscosity of the base oil at 100°C was 12.2 mm 2 /s.

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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)

Claims (3)

  1. Schmierfettzusammensetzung, umfassend Grundöl und als Verdickungsmittel Calciumkomplexseife und Lithiumseife, wobei die Schmierfettzusammensetzung dadurch gekennzeichnet ist, dass eine C18-22-geradkettige, substituierte oder unsubstituierte höhere Fettsäure, eine substituierte oder unsubstituierte aromatische Monocarbonsäure mit einem Benzolring und eine C2-4-geradkettige gesättigte Niedercarbonsäure als Carbonsäuren verwendet werden, die die Calciumkomplexseife und die Lithiumseife bilden,
    wobei, bezogen auf 100 Masseteile der gesamten gemischten Menge der Schmierfettzusammensetzung 3 bis 25 Masseteile der geradkettigen höheren Fettsäure, 0,3 bis 3 Masseteile der aromatischen Monocarbonsäure und 1 bis 5 Masseteile der geradkettigen gesättigten Niederfettsäure als Grund-Ausgangsmaterialien zugegeben sind und
    wobei das Massenverhältnis (Li/Ca) des Lithiummetallgehalts zu dem Calciummetallgehalt in dem Verdickungsmittel-Ausgangsmaterial 1 Teil pro 100 bis 5 Teile pro 100 beträgt.
  2. Schmierfettzusammensetzung gemäß Anspruch 1, wobei die geradkettige höhere Fettsäure wenigstens eine ausgewählt aus Stearinsäure, Oleinsäure, 12-Hydroxystearinsäure und Behensäure ist, die aromatische Monocarbonsäure wenigstens eine ausgewählt aus Benzoesäure und p-Toluylsäure ist und die geradkettige gesättigte Niederfettsäure wenigstens eine ausgewählt aus Essigsäure und Buttersäure ist.
  3. Verfahren zum Herstellen der Schmierfettzusammensetzung gemäß einem der Ansprüche 1 bis 2, umfassend den Schritt des Bildens von Calciumkomplexseife und Lithiumseife durch Zugeben der geradkettigen höheren Fettsäure, der aromatischen Monocarbonsäure, der geradkettigen gesättigten Niederfettsäure, von Calciumhydroxid und Lithiumhydroxid zu Grundöl.
EP13811953.2A 2012-12-21 2013-12-19 Schmierfettzusammensetzung Active EP2935539B1 (de)

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JP2012279391A JP6072532B2 (ja) 2012-12-21 2012-12-21 グリース組成物
PCT/EP2013/077491 WO2014096258A1 (en) 2012-12-21 2013-12-19 Grease composition

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CN104479832A (zh) * 2014-10-25 2015-04-01 中国石油化工股份有限公司 一种汽车装配线传送带专用润滑脂及制备方法
CN104450117A (zh) * 2014-10-25 2015-03-25 中国石油化工股份有限公司 一种汽车水泵轴承润滑脂组合物及制备方法
JP6744708B2 (ja) * 2015-01-21 2020-08-19 セイコーインスツル株式会社 転がり軸受用グリース、転がり軸受、転がり軸受装置及び情報記録再生装置
US10829714B2 (en) * 2016-06-23 2020-11-10 Jxtg Nippon Oil & Energy Corporation Grease composition for constant velocity joints, and constant velocity joint in which same is sealed
JP6712943B2 (ja) * 2016-12-01 2020-06-24 シェルルブリカンツジャパン株式会社 グリース組成物
CN106635348A (zh) * 2016-12-08 2017-05-10 新乡市恒星科技有限责任公司 一种船用螺旋桨润滑脂及其制备方法
JP6895863B2 (ja) * 2017-10-02 2021-06-30 シェルルブリカンツジャパン株式会社 グリース組成物
DE102018005835A1 (de) * 2018-07-24 2020-01-30 Klüber Lubrication München Se & Co. Kg Hybridfett mit niedrigen Reibwerten und hohem Verschleißschutz
JP7078508B2 (ja) * 2018-10-02 2022-05-31 出光興産株式会社 グリース組成物、及びグリース組成物の製造方法
CN110734805B (zh) * 2019-10-28 2022-11-22 中国石油化工股份有限公司 一种行星齿轮润滑脂
JP7455376B2 (ja) 2020-06-29 2024-03-26 株式会社ニッペコ グリース組成物
US11760952B2 (en) * 2021-01-12 2023-09-19 Ingevity South Carolina, Llc Lubricant thickener systems from modified tall oil fatty acids, lubricating compositions, and associated methods
CN112812874B (zh) * 2021-01-13 2022-09-13 北京航空工程技术研究中心 一种用于航空高温电机轴承的润滑脂
CN113201383B (zh) * 2021-05-14 2023-06-13 深高蓝德环保科技集团股份有限公司 一种生物降解润滑脂及制备方法
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WO2014096258A1 (en) 2014-06-26
BR112015014520A2 (pt) 2017-07-11
CN104870620A (zh) 2015-08-26
KR102127029B1 (ko) 2020-06-26
KR20150099565A (ko) 2015-08-31
JP2014122282A (ja) 2014-07-03
CN104870620B (zh) 2017-11-24
EP2935539A1 (de) 2015-10-28
US20150315509A1 (en) 2015-11-05
BR112015014520B1 (pt) 2020-12-15

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